- Gold Recovery from E-Waste by Porous Porphyrin-Phenazine Network Polymers
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Gold recovery from electronic waste could prevent excessive mining with toxic extractants and provide a sustainable path for recycling precious metals. Unfortunately, no viable recycling is practiced, except burning electronic circuit boards in underdevel
- Dogan, Nesibe A.,Hong, Yeongran,Nguyen, Thien S.,Yavuz, Cafer T.
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- Stable ultrathin films and hollow spheres fabricated from P(DSS-VP) and porphyrin derivatives
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Poly(4-diazosulfonate-styrene-4-vinylpyridine) (P(DSS-VP)), a new copolymer which possesses both photo-cross-linking and hydrogen accepting ability, was prepared and used to self-assemble (SA) with 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) or 5,
- Yang, Zhaohui,Yang, Linglu,Zhang, Maofeng,Cao, Weixiao
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- Highly Porous Metalloporphyrin Covalent Ionic Frameworks with Well-Defined Cooperative Functional Groups as Excellent Catalysts for CO2 Cycloaddition
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The development of multifunctional heterogeneous catalysts with high porosity and remarkable catalytic activity still remains a challenge. Herein, four highly porous metalloporphyrin covalent ionic frameworks (CIFs) were synthesized by coupling 5,10,15,20
- Liu, Jiahui,Zhao, Guoying,Cheung, Ocean,Jia, Lina,Sun, Zhenyu,Zhang, Suojiang
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- New nitrogen-rich azo-bridged porphyrin-conjugated microporous networks for high performance of gas capture and storage
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A series of new conjugated microporous polymers (Azo-1, Azo-2 and Azo-3) based on a nitrogen-rich porphyrin building unit and an azo bond linkage were synthesized by KOH assisted condensation. These materials were characterized by Fourier transform infrar
- Xu, Yanfei,Li, Zhi,Zhang, Fan,Zhuang, Xiaodong,Zeng, Zheng,Wei, Jianjun
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- A new and highly selective turn-on fluorescent sensor with fast response time for the monitoring of cadmium ions in cosmetic, and health product samples
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Cadmium (Cd) which is an extremely toxic could be found in many products like plastics, fossil fuel combustion, cosmetics, water resources, and wastewaters. It is capable of causing serious environmental and health problems such as lung, prostate, renal c
- Khani, Rouhollah,Ghiamati, Ebrahim,Boroujerdi, Ramin,Rezaeifard, Abdolreza,Zaryabi, Mohadeseh Hosseinpour
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- Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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The invention discloses a synthesis method of a tetra (4-aminophenyl) porphyrin metal complex. The method comprises the following steps: 1) taking organic acid as a solvent and pyrrole and 4-halogen benzaldehyde as substrates, and carrying out condensation reaction to obtain a (4-halogen phenyl) porphyrin solid; 2) dissolving the (4-halogen phenyl) porphyrin solid in an organic solvent, adding a metal salt, and reacting to obtain a (4-halogen phenyl) porphyrin metal complex; and 3) taking the (4-halophenyl) porphyrin metal complex and ammonia water as substrates, and carrying out carbon-nitrogen coupling reaction in the presence of a catalyst and an organic solvent to obtain the tetra (4-aminophenyl) porphyrin metal complex. The method is mild in reaction condition, low in toxicity, green and environment-friendly.
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Paragraph 0081-0083
(2021/06/13)
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- Interfacially synthesized 2D COF thin film photocatalyst: efficient photocatalyst for solar formic acid production from CO2and fine chemical synthesis
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The targeted synthesis of an efficient, visible light active, recyclable, freestanding covalent organic framework thin film photocatalyst for multi-faceted photocatalysis is the essence of the proposed work. A simple, scalable, reagent free synthesis of a thin film at the interface of 5,10,15,20-tetra-(4-aminophenyl)porphyrin, 2-vinylbenzene-1,4-dicarbaldehyde in nitrobenzene and aqueous glyoxal affords centimetre sized continuous 2D thin film with substantial stability, flexibility and efficient visible light activity. Strikingly different from the regular imine based COF, the incorporation of the glyoxal unit as a modulator helps in band gap tuning and induces flexibility within the thin film. An interplay between time and concentration helps in achieving a thin film photocatalyst with efficient photocatalytic activity for 1,4-NADH regeneration and selective formic acid formation from CO2. The optimum band edge position of the thin film photocatalyst also enables solar fine chemical synthesisviareductive dehalogenation under visible light illumination with excellent recyclability. The present work gives insight into visible light active thin film formation en route to metal-free sustainable photocatalysis.
- Yadav, Dolly,Kumar, Abhishek,Kim, Jae Young,Park, No-Joong,Baeg, Jin-Ook
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supporting information
p. 9573 - 9580
(2021/04/26)
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- Metalloporphyrin-based porous organic polymer as an efficient catalyst for cycloaddition of epoxides and CO2
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The chemical fixation of carbon dioxide to afford value added chemicals under solvent free and ambient conditions has gained considerable attentions. In this work, we successfully synthesized the porphyrin-based porous organic framework (PPOPs) through Schiff base reaction using 5,10,15,20-tetra(4-aminbiphenyl) porphyrin (TAPP) and 4,4′-biphenyldicarbaldehyde (BDA) as starting materials, which was then coordinated with cobalt to yield related metal complex (Co-PPOPs). The chemical structure and morphology of Co-PPOPs were characterized by absorption spectrum, FT-IR, X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and nitrogen physisorption. Co-PPOPs showed excellent catalytic activity towards the conversion of carbon dioxide to cyclic carbonates under ambient conditions. Furthermore, Co-PPOPs was recovered easily and could be used repeatedly (more than five times) without losing any catalytic activity. Thus, the as-prepared Co-PPOPs was a promising heterogeneous catalyst for carbon dioxide conversion, providing high turnover number than the previously reported catalysts.
- Guo, Ding,Li, Cheng,Liu, Genyan,Luo, Xiaogang,Wu, Fengshou,Zhang, Juan
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- Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction
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Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction (OER) is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin (Co-1-P) on carbon cloth (CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 mV. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.
- Zhang, Qingxin,Wang, Yabo,Wang, Yanzhi,Yang, Shujiao,Wu, Xuan,Lv, Bin,Wang, Ni,Gao, Yimei,Xu, Xiaoran,Lei, Haitao,Cao, Rui
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supporting information
p. 3807 - 3810
(2021/06/07)
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- Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two-Electron and Four-Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers
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Achieving a selective 2 e? or 4 e? oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αβαβ and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2), respectively, but ααββ and αααβ show poor selectivity with n=2.89–3.10. Isomer αβαβ catalyzes 2 e? ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e? ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e? and 4 e? ORR by tuning only steric effects without changing molecular and electronic structures.
- Apfel, Ulf-Peter,Cao, Rui,Guo, Kai,Jin, Xiaotong,Lei, Haitao,Li, Xialiang,Long, Ran,Lv, Bin,Ma, Jun,Wang, Fang,Wang, Yanzhi,Xiong, Yujie,Zhang, Qingxin,Zhang, Wei
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supporting information
p. 12742 - 12746
(2021/04/22)
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- Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal-Organic Cages
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To illustrate the supramolecular catalysis process in molecular containers, two porphyrinatozinc(II)-faced cubic cages with different sizes were synthesized and used to catalyze acyl-transfer reactions between N-acetylimidazole (NAI) and various pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC). A systemic investigation of the supramolecular catalysis occurring within these two hosts was performed, in combination with a host-guest binding study and density functional theory calculations. Compared to the reaction in a bulk solvent, the results that the reaction of 2-PC was found to be highly efficient with high rate enhancements (kcat/kuncat = 283 for Zn-1 and 442 for Zn-2), as well as the different efficiencies of the reactions with various ortho-substituted 2-PC substrates and NAI derivates should be attributed to the cages having preconcentrated and preoriented substrates. The same cage displayed different catalytic activities toward different PC regioisomers, which should be mainly attributed to different binding affinities between the respective reactant and product with the cages. Furthermore, control experiments were carried out to learn the effect of varying reactant concentrations and product inhibition. The results all suggested that, besides the confinement effect caused by the inner microenvironment, substrate transfer, including the encapsulation of the reactant and the release of products, should be considered to be a quite important factor in supramolecular catalysis within a molecular container.
- Li, Lili,Yang, Linlin,Li, Xuezhao,Wang, Jing,Liu, Xin,He, Cheng
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supporting information
p. 8802 - 8810
(2021/06/28)
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- Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic Frameworks for Catalytic CO2Cycloaddition via Visible-Light-Induced Photothermal Conversion
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We report the construction of a porphyrin and imidazolium-ionic liquid (IL)-decorated and quinoline-linked covalent organic framework (COF, abbreviated as COF-P1-1) via a three-component one-pot Povarov reaction. After post-synthetic metallization of COF-P1-1 with Co(II) ions, the metallized COF-PI-2 is generated. COF-PI-2 is chemically stable and displays highly selective CO2 adsorption and good visible-light-induced photothermal conversion ability (ΔT = 26 °C). Furthermore, the coexistence of Co(II)-porphyrin and imidazolium-IL within COF-PI-2 has guaranteed its highly efficient activity for CO2 cycloaddition. Of note, the needed thermal energy for the reactions is derived from the photothermal conversion of the Co(II)-porphyrin COF upon visible-light irradiation. More importantly, the CO2 cycloaddition herein is a "window ledge"reaction, and it can proceed smoothly upon natural sunlight irradiation. In addition, a scaled-up CO2 cycloaddition can be readily achieved using a COF-PI-2@chitosan aerogel-based fixed-bed model reactor. Our research provides a new avenue for COF-based greenhouse gas disposal in an eco-friendly and energy- and source-saving way.
- Ding, Luo-Gang,Yao, Bing-Jian,Wu, Wen-Xiu,Yu, Zhi-Gao,Wang, Xiao-Yu,Kan, Jing-Lan,Dong, Yu-Bin
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supporting information
p. 12591 - 12601
(2021/08/24)
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- Amino-metalloporphyrin polymers derived Fe single atom catalysts for highly efficient oxygen reduction reaction
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Recently, nitrogen-doped porous carbon supported single atom catalysts (SACs) have become one of the most promising alternatives to precious metal catalysts in oxygen reduction reaction (ORR) due to their outstanding performance, especially those derived from porphyrin-based materials. However, most of them involve other metal residuals, which would cause the tedious pre- and/or post-treatment, even mislead the mechanistic investigations and active-site identification. Herein, we report a precursor-dilution strategy to synthesize Fe SACs through the Schiff-based reaction via co-polycondensation of amino-metalloporphyrin, followed by pyrolysis at high temperature. Systematic characterization results provide the compelling evidence of the dominant presence of atomically dispersed Fe-Nx species. Our catalyst shows superior ORR performance with positive half-wave potential (E1/2=0.85 V vs. RHE) in alkaline condition and moderate activity (E1/2=0.68 V vs. RHE) under the acidic condition, excellent methanol tolerance and good long-term stability. All the results indicate Fe SACs would be a promising candidate for replacing the precious Pt in metal-air batteries and fuel cells.
- Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Meng, Yuying,Sun, Qingdi,Xiao, Huajian,Zhang, Hao,Zhang, Ying
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p. 810 - 817
(2020/06/05)
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- Improved Photoreduction of CO2 with Water by Tuning the Valence Band of Covalent Organic Frameworks
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Porous covalent organic frameworks (COFs), as an emerging material, have the characteristics of high stability, large series of components, easy synthesis, modification, and adjustable amplitude. They have the potential to become good catalysts. Bromine, as a halogen, has attracted intensive interest for the modification of photocatalysts for photocatalytic reactions. It is feasible to enhance the activity and selectivity of the material by facile functionalization of the reticular parent structure′s electron-withdrawing groups. In addition, the conjugation effect of bromine, further delocalizing the electrons of the COF, is beneficial to the progress of many photocatalytic reactions. Reports on the modification of COFs by bromine functional groups to improve the catalytic performance have not been found so far. Here, TAPP [5,10,15,20-tetrakis(4-aminophenyl)porphyrin] and 2,5-dibromo-1,4-benzenedialdehyde instead of terephthalaldehyde were chosen to synthesize a porphyrin-based COF (TAPBB-COF) by the solvothermal method. As expected, the valence band (VB) of TAPBB-COF is thus adjusted to a more suitable position. Additionally, the CO production when using TAPBB-COF under full-wavelength light for 12 h was 295.2 μmol g?1, which was three times that of COF-366, and the new material has good recycling stability and selectivity (95.6 %). Theoretical calculations indicate that the nitrogen of the porphyrin ring and the Schiff base, and the bromine in TAPBB-COF contribute greatly to the activation of H2O and the conversion of CO2 in the photoreaction.
- Wang, Lu-jie,Wang, Rui-lei,Zhang, Xiao,Mu, Jing-lin,Zhou, Zi-yan,Su, Zhong-min
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p. 2973 - 2980
(2020/04/23)
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- Specific porphyrin self-transport nano carrier material and preparation method thereof
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The invention relates to a preparation method of a specific porphyrin self-transport nano carrier material. The method comprises the following steps of carrying out a mixed reaction on p-nitrobenzaldehyde, acetic anhydride, propionic acid and pyrrole to obtain purple solid tetra(4-nitrophenyl)porphyrin TNPP, and preparing tetra(4-aminophenyl)porphyrin TAPP; stirring TPGS, succinic anhydride, DMAP,triethylamine and 1,4-dioxane at room temperature, and performing dialysis to obtain carboxyl TPGS; and mixing the carboxyl TPGS, DMAP and PyBOP, adding DMF and TAPP, performing stirring at room temperature for 22-26 hours, performing dialysis, and freeze-drying dialysate to obtain the product TAPP-TPGS. The specific molecules TPGS are introduced into the carrier material, so that the carrier hasthe effect of assisting an anti-tumor drug in treating cancers, and the anti-tumor effect is improved through combined treatment of three modes of TPGS, PDT and chemotherapy.
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Paragraph 0015
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- Encapsulation of Flavin Cofactor within a Manganese Porphyrin-Based Metal-Organic Polyhedron for Reductive Dioxygen Activation
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Encapsulation of flavin mononucleotide (FMN) in a porphyrinatomanganese(III)-based cubic cage allowed the fast reduction of manganese(III) porphyrin in the presence of nicotinamide adenine dinucleotide (NADH). This supramolecular system was capable of efficiently activating dioxygen and catalyzing the oxidation of benzyl alcohol. Control experiments suggested that the close proximity between FMN and manganese(III) porphyrins forced by the host-guest interaction might benefit the electron-transfer process from the FMN cofactor to the metal centers.
- Guo, Huimin,He, Cheng,Li, LiLi,Li, Xuezhao,Wang, Hailing,Yang, Linlin
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supporting information
p. 2636 - 2640
(2020/03/19)
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- Donor-acceptor covalent organic frameworks of nickel(ii) porphyrin for selective and efficient CO2reduction into CO
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Donor-acceptor two-dimensional covalent organic frameworks, PD-COF-23 and PD-COF-23-Ni, are constructed and applied for selective CO2 reduction with CO conversion rates of 20.9 μmol g-1 h-1 and 40.0 μmol g-1 h-1, respectively, in the absence of any additional photosensitizers and noble metal co-catalysts within an operation time of 25 h. The multilayer nanosheet structure, efficient charge separation and transport, and internal reductive quenching cycle of the NiTAPP fragments of PD-COF-23-Ni result in its higher photocatalytic efficiency than that of PD-COF-23. This journal is
- Diao, Yingxue,Ke, Hanzhong,Qin, Xihao,Xu, Nanfeng,Xu, Zhengtao,Zhu, Xunjin
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supporting information
p. 15587 - 15591
(2020/11/24)
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- Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks
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Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+ in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O2 to 1O2 and O2?-, respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O2?-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in 1O2-mediated selective oxidation of organic sulfides. This work provides in-depth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
- Qian, Yunyang,Li, Dandan,Han, Yulan,Jiang, Hai-Long
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supporting information
p. 20763 - 20771
(2020/12/23)
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- Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O
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Solar energy-driven conversion of CO2 into fuels with H2O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO2 with H2O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO2 reduction and H2O oxidation. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H2O oxidation to O2. Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.
- Lu, Meng,Liu, Jiang,Li, Qiang,Zhang, Mi,Liu, Ming,Wang, Jin-Lan,Yuan, Da-Qiang,Lan, Ya-Qian
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supporting information
p. 12392 - 12397
(2019/08/16)
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- In situ bottom-up synthesis of porphyrin-based covalent organic frameworks
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Synthesis and processing of two-or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.
- Tavakol, Elham,Kakekhani, Arvin,Kavani, Shayan,Tan, Peng,Ghaleni, Mahdi Mohammadi,Zaeem, Mohsen Asle,Rappe, Andrew M.,Nejati, Siamak
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supporting information
p. 19560 - 19564
(2019/12/24)
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- Porphyrin-containing Polyimide with Enhanced Light Absorption and Photocatalysis Activity
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A series of porphyrin-containing polyimide (PI) photocatalysts were synthesized by a one-step solvothermal method. Characterization results revealed that porphyrin was uniformly coupled into the PI framework through covalent bonding and the visible-light absorption was greatly improved. The photodegradation activity of porphyrin-containing PIs for methyl orange (MO) under visible light was enhanced significantly, with the highest pseudo-first-order rate constant 35 times higher than that of neat porphyrin and 10 times higher than that of porphyrin-free PI. The enhancement is mainly attributed to an increased light harvesting accompanied by a varied HOMO level, which was clarified by control experiments, characterizations and theoretical calculations. This work provides an insight into multiple effects of dye molecules in dye-containing heterogeneous photocatalysts.
- Cui, Zhiwei,Zhou, Jun,Liu, Teng,Wang, Yicong,Hu, Yue,Wang, Ying,Zou, Zhigang
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supporting information
p. 2138 - 2148
(2019/05/27)
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- A novel one-dimensional porphyrin-based covalent organic framework
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A novel one-dimensional covalent organic framework (COF-K) was firstly designed and synthesized through a Schiff-based reaction from a porphyrin building block and a nonlinear right-angle building block. The COF-K exhibited high BET surface area and narrow pore size of 1.25 nm and gave a CO2 adsorption capacity of 89 mg g?1 at 273K and 1bar.
- Zhang, Miao,Zheng, Ruijin,Ma, Ying,Chen, Ruiping,Sun, Xun,Sun, Xuan
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- Covalently Copper(II) Porphyrin Cross-Linked Graphene Oxide: Preparation and Catalytic Activity
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Abstract: In this study, copper(II)-coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (CuPPh) as a macrocyclic copper complex was covalently linked to the surface of graphene oxide (GO–CuPPh). This covalently cross-linked catalyst was characterized with various analysis such as FT-IR, SEM, TEM, EDS, ICP, TGA and UV–Vis. All analysis confirm the successful covalently immobilization of CuPPh on the GO. Then, the activity of catalyst has been tested for the preparation of propargylamine derivatives by the reaction of different aldehydes/ketones various amines and phenylacetylene via A3 and KA2 coupling reactions. The catalytic system indicated great catalytic activity in this reaction and the yields of the products were good to marvelous. The results of this work are hoped to aid the establishment of new class of heterogeneous catalysts as the high performance and low-cost candidates for industrial applications. Graphical Abstract: [Figure not available: see fulltext.].
- Khojastehnezhad, Amir,Bakavoli, Mehdi,Javid, Ali,Khakzad Siuki, Mohammad Mehdi,Moeinpour, Farid
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p. 713 - 722
(2019/02/03)
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- Zirconium (IV) porphyrin graphene oxide: a new and efficient catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones
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A covalently cross-linked graphene oxide (GO) as a catalyst was prepared by a cross-linking process using the nucleophilic reaction of zirconium (IV)-coordinated 5,10,15,20-tetrakis (aminophenyl)porphyrin (ZrPPh) with carboxyl groups of the edges of GO (GO-ZrPPh). The chemical structure of catalyst was characterized by different analyses such as FT-IR, SEM, TEM, EDS, ICP, TGA and UV. All analyses confirm the occurrence of successfully covalent immobilization of ZrPPh on the GO. Also, TEM and SEM images show that ZrPPh has been immobilized in the both of the edges and the basal plane of GO. The activity of the catalyst was studied for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones via Biginelli reaction. The cross-linked catalyst is able to catalyze the reaction in short reaction times and good to excellent yields.
- Ghadamyari, Zohreh,Shiri, Ali,Khojastehnezhad, Amir,Seyedi, Seyed Mohammad
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- Three-dimensional porphyrin-based covalent organic frameworks with tetrahedral building blocks for single-site catalysis
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Two three-dimensional (3D) porphyrin covalent organic frameworks, PCOF-1 and PCOF-2, were synthesized via imine condensation of a planar porphyrin tetramine (TAPP or TABPP) and a rigid tetrahedral aldehyde based on the steric hindrance of 3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl (TFBM). The structures of PCOF-1 and PCOF-2 were studied by FT-IR and 13C CP-MAS solid state NMR spectroscopy. Powder X-ray diffraction patterns revealed obvious crystallinity with two intense peaks at 3.28° and 3.75° for PCOF-1, and 2.63° and 2.98° for PCOF-2. Structural simulation confirmed their 3D rutile type (pts) topological structures with two different pore sizes. X-ray single crystal diffraction revealed a distorted tetrahedral structure for the building block TFBM with two dihedral angles of 119° and 107.8°, and a planar square structure for the model compound (MC) with an outspread angle of 176.5°. PCOF-1 and PCOF-2 exhibited Brunauer-Emmett-Teller (BET) surface areas of 316 and 234 m2 g-1, respectively. The morphologies of PCOF-1 and PCOF-2 were investigated by scanning electron microscopy and transmission electron microscopy methods. PCOF-1 and PCOF-2 showed a high thermal stability up to 420 °C without decomposition through thermogravimetric analysis (TGA), and high chemical stability with no obvious mass loss after three days of immersion in various solutions. Due to the large surface area and the appropriate pore size, PCOF-Fe exhibited excellent biocatalytic catalytic performance, while PCOF-Co exhibited good electrocatalytic activity towards oxygen evolution reactions. These results indicate that 3D porphyrin-based COFs constructed from the tetrahedral building block with steric hindrance are promising candidates for single-site catalysis.
- Liu, Yong,Yan, Xiaodong,Li, Tao,Zhang, Wen-Da,Fu, Qiu-Ting,Lu, Hui-Shu,Wang, Xuan,Gu, Zhi-Guo
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supporting information
p. 16907 - 16914
(2019/11/14)
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- Temperature-responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide
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The selective synthesis of polypropylene carbonate (PPC) and cyclic propylene carbonate (CPC) from coupling reaction of CO2 and propylene oxide (PO) is a long term pursuing target. Here we report that a temperature controllable porphyrin alumin
- Zhuo, Chunwei,Qin, Yusheng,Wang, Xianhong,Wang, Fosong
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p. 299 - 305
(2018/02/21)
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- In silico study, synthesis, and cytotoxic activities of porphyrin derivatives
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Five known porphyrins, 5,10,15,20-tetrakis(p-tolyl)porphyrin (TTP), 5,10,15,20-tetrakis(pbromophenyl) porphyrin (TBrPP), 5,10,15,20-tetrakis(p-aminophenyl)porphyrin (TAPP), 5,10,15- tris(tolyl)-20-mono(p-nitrophenyl)porphyrin (TrTMNP), 5,10,15-tris(tolyl)-20-mono(paminophenyl) porphyrin (TrTMAP), and three novel porphyrin derivatives, 5,15-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-10,20-di(p-tolyl)porphyrin (DBECPDTP), 5,10-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-15,20-di-(methylpyrazole-4-yl)porphyrin (cDBECPDPzP), 5,15-di- [bis(3,4-ethylcarboxymethylenoxy)phenyl]-10,20-di-(methylpyrazole-4-yl)porphyrin (DBECPDPzP), were used to study their interaction with protein targets (in silico study), and were synthesized. Their cytotoxic activities against cancer cell lines were tested using 3-(4,5-dimetiltiazol-2-il)-2,5- difeniltetrazolium bromide (MTT) assay. The interaction of porphyrin derivatives with carbonic anhydrase IX (CAIX) and REV-ERBβ proteins were studied by molecular docking and molecular dynamic simulation. In silico study results reveal that DBECPDPzP and TrTMNP showed the highest binding interaction with REV- ERBβ and CAIX, respectively, and both complexes of DBECPDPzPREV- ERBβ and TrTMNP-CAIX showed good and comparable stability during molecular dynamic simulation. The studied porphyrins have selective growth inhibition activities against tested cancer cells and are categorized as marginally active compounds based on their IC50.
- Kurniawan, Fransiska,Miura, Youhei,Kartasasmita, Rahmana Emran,Mutalib, Abdul,Yoshioka, Naoki,Tjahjono, Daryono Hadi
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- Electrochemical hydrogen evolution by cobalt (II) porphyrins: Effects of ligand modification on catalytic activity, efficiency and overpotential
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Electrochemical H2 evolution of a series of cobalt(II) porphyrins with electron-withdrawing (EW) and electron-donating (ED) substituents at the para positions of the meso-phenyl rings has been investigated in DMSO using acetic acid as a proton source. Our study showed that the nature of substituents significantly influences catalytic activity, efficiency, and the potential at which catalysis occurs. Faradaic efficiencies (FE) ranging from 44 to 99%, turnover numbers (TONs) from 1.5 to 104 (~11 h electrolysis), turnover frequencies (TOFs) from 0.23 to 9.1 h?1, and onset overpotentials from 25 to 445 mV were obtained by tuning the porphyrinic substituents. Cobalt porphyrins with -SO3H, -COOH, or -NH2 groups as the substituents showed high activity and efficiency with more positive onset potentials as compared to the parent [Co(TPP)]. Supports also from the low hydrogen generation activities for complexes with -COOMe, -OMe and -OH groups as the substituents suggest that the acidity of the meso-phenyl substituent plays a key role in enhancing the hydrogen evolution activities during the catalytic processes.
- Beyene, Belete B.,Mane, Sandeep B.,Hung, Chen-Hsiung
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p. H481 - H487
(2018/07/06)
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- Synthesis, characterization and first application of covalently immobilized nickel-porphyrin on graphene oxide for Suzuki cross-coupling reaction
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In this study, nickel(ii)-coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (NiTAPP) as a macrocyclic complex was covalently grafted to the edge of graphene oxide (GO). The prepared nanocatalyst was well characterized by various techniques such as FT-IR, Raman, XRD, TEM, SEM, EDX, TGA, ICP-OES, UV and XPS. All analyses confirmed the successful immobilization of NiTAPP on GO. The synthesized catalyst was applied to evaluate its performance in the Suzuki-Miyaura cross-coupling reaction. GO/NiTAPP exhibited good catalytic efficiency with a high yield of products. Moreover, the suggested catalyst could be recycled for five consecutive cycles without a noticeable decrease in its catalytic activity or metal leaching.
- Keyhaniyan, Mahdi,Shiri, Ali,Eshghi, Hossein,Khojastehnezhad, Amir
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p. 19433 - 19441
(2018/12/13)
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- Synthetic method of porphyrin and porphyrin derivative
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The invention discloses a synthetic method of porphyrin and a porphyrin derivative. According to the method, a reaction separation synchronous reactor is used to prepare porphyrin and the porphyrin derivative. The reaction separation synchronous reactor includes a stirring reaction tower and a constant-temperature settlement tower connected to the bottom of the stirring reaction tower. The method comprises: adding a mixed raw material of pyrrole, a benzaldehydes compound, organic carboxylic acid and DMF in the reaction separation synchronous reactor till the reaction zone of the constant-temperature settlement tower and the stirring reaction tower is filled with the mixed raw material, controlling the temperature in the stirring reaction tower in a range of 130-155 DEG C and controlling the temperature of the constant-temperature settlement tower in a range of 50-80 DEG C, and obtaining the porphyrin or porphyrin derivative precipitation from the constant-temperature settlement tower. According to the method, no complicated separation means is adopted, and high-purity porphyrin is obtained at a high yield. The method allows industrial production to be easily achieved.
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Paragraph 0037-0038; 0047-0050
(2017/07/21)
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- Method for synthesizing TNPP and TAPP at high yield and high efficiency
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The invention provides a method for synthesizing TNPP and TAPP at high yield and high efficiency and belongs to the technical field of chemical synthesis. The method provided by the invention is characterized in that a small amount of acetic anhydride or propionic anhydride is added to serve as a catalyst in the reaction process of nitrobenzaldehyde and pyrrole, so that the reaction speed is effectively improved and the reaction is performed rightwards to the maximum extent; hot pyrrole is adopted for dissolving and purifying the TNPP to obtain a TNPP product with high purity; in the process of synthesizing the TAPP, a strong reducer tin chloride is adopted for ammonifying the TNPP, and trichloromethane capable of dissolving the TAPP is adopted for efficiently separating the TAPP from an organic phase by adopting a Soxhlet extraction method, so that the purity and the yield of the TAPP are effectively improved.
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Paragraph 0019; 0020
(2017/09/02)
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- Novel nanostructured smart, photodynamic hydrogels based on poly(N-isopropylacrylamide) bearing porphyrin units in their crosslink chains: A potential sensitizer system in cancer therapy
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Novel nanostructure, pH-thermo dual responsive photodynamic hydrogels based on poly(N-isopropylacrylamide) were successfully synthesized by in situ dispersion polymerization of NIPAAm with 5,10, 15, 20-tetrakis(4-N-carbonylacrylic aminophenyl)porphyrin (2% and 4% w/w) in the presence of methylene-bis-acrylamide (MBA) in water. 5, 10, 15, 20-tetrakis (4-N-carbonylacrylic aminophenyl)porphyrin (CAA-TPP) was designed and synthesized for the first time via reaction of tetrakis(4-aminophenyl)porphyrin (NH2-TPP) with maleic anhydrid and was applied as a crosslinker. The structure of the 5, 10, 15, 20-tetrakis(4-N-carbonylacrylic aminophenyl) porphyrin and hydrogels was thoroughly studied by a variety of techniques such as NMR, FT-IR and UV–visible spectrophotometer. The surface morphology of freeze-dried hydrogels using SEM showed one-dimensional nanostructured with uniform morphology of self-assembled interconnected nanofibers. Rheological measurement results were showed that the incorporation of porphyrin onto polymer structure can provide hydrogels without the loss of thermoresponsive viscoelastic properties. The lower critical solution temperatures (LCST) of P[NIPAAm-co-CAA-TPP] hydrogels in water were measured by the cloud point (CP) method. The LCST of P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] were at about 40 °C and 43 °C, respectively. The results showed that an increase in porphyrin content makes the LCSTs of the hydrogels increase. Swelling measurements of hydrogels indicated sensitivity to temperature and pH, suggesting that the P[NIPAAm-co-CAA-TPP]s were temperature/pH dual stimulus-responsive hydrogels. In this work, the efficiency of P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] as photodynamic therapy (PDT) systems were investigated. The production of reactive singlet oxygen, cytotoxity and phototoxicity of them were assessed. The study showed that the singlet oxygen production ability of P[NIPAAm-co-CAA-TPP (2%)] can be well controlled by irradiation time compared with free porphyrin. We tested these two hydrogels on A453 cells to compare their effectiveness. P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] exhibited cell viability over 97% and good photocytotoxity, indicating they are promising photodynamic systems for cancer therapy.
- Belali, Simin,Karimi, Ali Reza,Hadizadeh, Mahnaz
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- Tetramine monomer of hyperbranched polyimide containing porphyrin structure, hyperbranched polyimide polymer, preparation method and application
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The invention discloses a tetramine monomer of hyperbranched polyimide containing a porphyrin structure, a hyperbranched polyimide polymer, a preparation method and an application and belongs to the technical field of preparation of hyperbranched polyimide. The anhydride-terminated or amino-terminated hyperbranched polyimide material is synthesized from TAPP serving as polyamine and dianhydride. The TAPP has a large conjugated molecule system to form a two-dimensional coplanar structure, can form a stable spatial network structure with dianhydride easily and has great application prospects as a photoelectrical material. Besides, the hyperbranched polyimide formed by TAPP and dianhydride can be applied to the field of porous adsorbent materials.
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Paragraph 0039; 0040; 0041; 0042
(2017/09/02)
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- PH-sensitive fluorescent dye and its preparation method and application
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The invention discloses pH sensitive fluorochrome and a preparation method and application thereof. The molecule in the pH sensitive fluorochrome contains two fluorophores responded to pH, the molecular structural formula of the pH sensitive fluorochrome is shown in the formula I, M is selected from NH2 or -COOH, R is selected from -(CH2)n- or -Ph-, and n is larger than or equal to 2 and is smaller than or equal to 4. The pH sensitive fluorochrome is prepared by connecting a naphthalimide derivative with a porphyrin derivative through a Schiff base reaction. When M is -NH2, aliphatic dialdehyde or aromatic dialdehyde is used as a connection bridge; when M is -COOH, aliphatic linear chain diamide or p-phenyl diamide is used as a connection bridge. The pH sensitive fluorochrome can be used for manufacturing a fluorescence ratio sensor. The pH sensitive fluorochrome is high in sensitivity, good in selectivity, photo-stable and high in quantum yield.
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Paragraph 0055
(2018/01/13)
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- Novel graphene capsule-aminoporphyrin nanohybrids: Preparation and application in photodynamic therapy of cancer
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In this work, we firstly prepared new sealed graphene capsules (GCs) that were about 300 nm in size and had different morphologies using a simple reduction method. The quality of the graphene oxide (GO) sheets and the concentration of hydrazine hydrate are proposed to be influencing factors for the formation of sealed graphene capsules. GCs are covalently functionalized with 5,10,15,20-tetra-(4-aminophenyl)porphyrin, forming dispersible GC-aminoporphyrins in aqueous solution. The observed fluorescence quenching of the GCs by the aminoporphyrin indicated that the GCs are electron donors and electron transfer occurs from the GCs to the aminoporphyrin. This F?rster Resonance Energy Transfer (FRET) between the GCs and aminoporphyrins is probably the reason for the enhancement of 1O2 generation of the GC-aminoporphyrins. More importantly, the as-prepared GC-aminoporphyrin nanohybrids as novel photosensitizers (PSs) with a short excitation wavelength can be used as PDT reagents for the treatment of malignant melanoma A375 with high efficiency. We expect that GC-aminoporphyrins will be promising PSs in future cancer therapy.
- Liu, Guoli,Lv, Hongying,Zhao, Jing,Zhang, Shen,Sun, Shuqing
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p. 56062 - 56072
(2017/12/26)
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- Synthesis and Properties of Isoindoline Nitroxide-containing Porphyrins
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Isoindoline nitroxide-containing porphyrins were synthesized by the reaction of 5-phenyldipyrromethane and 5-(4′-nitrophenyl)-dipyrromethane with 5-formyl-1,1,3,3-tetramethylisoindolin-2-yloxyl using the Lindsey method. These spin-labeled porphyrins were
- Liu, Fan,Shen, Yan-Chun,Ouyang, Yao-Hua,Yan, Guo-Ping,Chen, Si,Liu, Hui,Wu, Yan-Guang,Wu, Jiang-Yu
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p. 3143 - 3151
(2017/10/06)
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- Novel porphyrin-Schiff base conjugates: Synthesis, characterization and: In vitro photodynamic activities
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Three novel porphyrin-Schiff base conjugates derived from tetra(4-aminophenyl)porphyrin (TAPP), namely, tetra[4-(4-hydroxy benzylideneamino)]phenyl porphyrin (3a), tetra[4-(2-thienyldeneamino)]phenyl porphyrin (3b) and tetra[4-(2-pyridyldeneamino)]phenyl porphyrin (3c), were synthesized and characterized by IR, UV-vis, 1H NMR, HRMS and elementary analysis. Their biological activities against human epidermoid carcinoma (A431) cells were evaluated with an MTT assay. As we expected, the porphyrin conjugates showed negligible cytotoxicity to A431 cells in the absence of light, while their phototoxic activities were improved after irradiated with LED lamp (425 nm) and increased significantly with increased doses. The fluorescence microscope pictures revealed that the three porphyrin-Schiff conjugates could diffuse into skin cancer cells, demonstrating that these compounds are potential candidates for photodynamic therapy agents.
- Yao, Ya-Hong,Li, Jun,Yuan, Long-Fei,Zhang, Zeng-Qi,Zhang, Feng-Xing
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p. 45681 - 45688
(2016/06/06)
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- Synthesis and characterization of tetraarylporphyrins in the presence of nano-TiCl4·SiO2
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[MediaObject not available: see fulltext.] Synthesis of tetraarylporphyrins by the coupling of an aromatic aldehyde and pyrrole using nano-TiCl4·SiO2 as mild, inexpensive, and highly efficient catalyst is studied in the present article.
- Zamani, Leila,Mirjalili, Bi Bi Fatemeh
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p. 578 - 581
(2016/02/16)
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- Synthesis, characterization and in vitro photodynamic antimicrobial activity of basic amino acid-porphyrin conjugates
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Photodynamic antimicrobial chemotherapy (PACT), as a novel and effective modality for the treatment of infection with the advantage of circumventing multidrug resistance, receives great attention in recent years. The photosensitizer is the crucial element in PACT, and cationic porphyrins have been demonstrated to usually be more efficient than neutral and negatively charged analogues towards bacteria in PACT. In this work, three native basic amino acids, l-lysine, l-histidine and l-arginine, were conjugated with amino porphyrins as cationic auxiliary groups, and 13 target compounds were synthesized. This paper reports their syntheses, structural characterizations, oil-water partition coefficients, singlet oxygen generation yields, photo-stability, as well as their photo inactivation efficacies against methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli and Pseudomonas aeruginosa in vitro. The preliminary structure-activity relationship was discussed. Compound 4i, with porphyrin bearing four lysine moieties, displays the highest photo inactivation efficacy against the tested bacterial strains at 3.91 1/4M with a low light dose (6 J/cm2), and it is stable in serum and lower cytotoxicity to A929 cells. These basic amino acid-porphyrin conjugates are potential photosensitizers for PACT.
- Meng, Shuai,Xu, Zengping,Hong, Ge,Zhao, Lihui,Zhao, Zhanjuan,Guo, Jianghong,Ji, Haiying,Liu, Tianjun
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supporting information
p. 35 - 48
(2015/02/19)
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- Directing two azo-bridged covalent metalloporphyrinic polymers as highly efficient catalysts for selective oxidation
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Manganese meso-tetra (4-nitrophenyl)porphyrin (Mn-TNPP) with four nitro groups at periphery was employed as building moieties to condense with p-phenylenediamine and benzidine into extended π materials, respectively. Two covalent metalloporphyinic polymer
- Zhang, Weijie,Jiang, Pingping,Wang, Ying,Zhang, Jian,Zhang, Pingbo
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p. 117 - 122
(2015/05/05)
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- Highly sensitive INHIBIT and XOR logic gates based on ICT and ACQ emission switching of a porphyrin derivative
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Fluorescence-switch-based logic devices are very sensitive compared with most of the reported devices based on UV/Vis absorption systems. Herein, we demonstrate that a simple molecule, 5,10,15,20-tetra-(4-amino-phenyl) porphyrin (TAPP), shows protonation-induced multiple emission switches through intramolecular charge transfer and/or aggregation-caused quenching. Highly sensitive INHIBIT and XOR logic gates can be achieved by combining the intermolecular assembly with the intramolecular photoswitching of diprotonated TAPP (TAPPH22+). In addition, molecular simulations have been performed by DFT for a better understanding of the emission-switching processes.
- Xu, Xiao-Ling,Lin, Fu-Wen,Xu, Wei,Wu, Jian,Xu, Zhi-Kang
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supporting information
p. 984 - 987
(2015/03/05)
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- Two self-assemblies of Schiff base porphyrins to modify titanium dioxide electrodes for supramolecular solar cells
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Abstract In this work, two Schiff base porphyrins have been successfully synthesized. The metal-ligand axial coordination assembling strategy has been used to organize two assemblies based on the two porphyrins appended isonicotinic acid ligands. Further, the assemblies were absorbed on the semiconducting TiO2 electrode surfaces by the carboxylic groups of isonicotinic acid ligands, and their photovoltaic performances were performed under irradiance of 100 mW cm-2 AM 1.5G sunlight. Photoelectrochemical studies show a significantly enhanced photovoltaic behavior for phenol-based zinc porphyrin assembly compared to pyridine-based zinc porphyrin assembly. The UV-Vis absorption, fluorescence spectra, molecular orbital patterns, and HOMO-LUMO energy gaps of the assemblies were also performed to further understand their photovoltaic features. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy.
- Wu, Yu,Liu, Jia-Cheng,Cao, Jing,Li, Ren-Zhi,Jin, Neng-Zhi
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p. 6833 - 6842
(2015/08/18)
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- Biomimetic Nitration of Phenols Using Metalloporphyrins/H2O2/NO2 -
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An efficient metalloporphyrins/H2O2/NO2 - nitration of phenols has been developed. The total yield of nitrophenol could reach up to 55.1 %, which is about 4 and sixfold higher than that of horse radish peroxidase catalysis and peroxynitrite nitration, respectively. Furthermore, the nitration system attained an enhanced regioselectivity of 1.0 o/p ratio, and exhibited a good substrate scope of monophenols. This protocol is environmentally friendly compared with HNO3/H2SO4 nitration, and stable, inexpensive and organic solvent tolerant compared with enzyme catalytic nitration and peroxynitrite nitration reaction. Graphical Abstract: [Figure not available: see fulltext.]
- Sun, Weizhi,Liu, Yaojie,Zhang, Haibo,Xian, Mo,Liu, Huizhou
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p. 1991 - 1999
(2015/12/24)
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- Porphyrin-vancomycin: A highly promising conjugate for the identification and photodynamic inactivation of antibiotic resistant Gram-positive pathogens
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The emergence of drug-resistant pathogens is a global public health problem. With the increasing antibiotic resistance of bacteria, there is an obvious need for the development for alternative therapeutics and materials that can effectively control this situation. In this work, a new conjugate, 5,10,15,20-tetrakis (para-aminophenyl) porphyrin-vancomycin was successfully explored for the identification and photoinactivation of antibiotic resistant Gram-positive pathogens. The minimum inhibitory concentration assay and photodynamic inactivation evaluation results revealed that the conjugate can effective inhibit the growth of 6 tested pathogenic strains under white light. The interaction intensity of the conjugate with Gram-positive and Gram-negative bacterial cells was evaluated by surface plasmon resonance, and the results showed that its activity toward Staphylococcus aureus was 14-fold larger than its activity toward Escherichia coli at 20 mM, indicating the conjugate selectively gathers in Gram-positive cells.
- Zhai, Le,Yang, Ke-Wu
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p. 228 - 238
(2015/05/13)
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- Effects of substituents on the photophysical properties of symmetrical porphyrins
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Porphyrin compounds having groups that mimic the phenolic moiety of m- and p-isomers of 5,10,15,20-tetrakis(hydroxyphenyl) porphyrin (THPP) have been synthesized along with 5,10,15,20-tetrakis(heteroaryl) porphyrins bearing 2-thienyl and 5-thiazolyl groups. Absorption and fluorescence spectroscopy, including fluorescence lifetime (τf) and quantum yield (Φf) measurements, were employed to characterize the singlet excited state of all compounds, using 5,10,15,20-tetraphenylporphyrin (H 2TPP) as a standard (Φf = 0.12 in DMF). The generation of singlet oxygen by each porphyrin photosensitizer was measured as the singlet oxygen quantum yield (ΦΔ), using H2TPP as a standard (ΦΔ = 0.64 in DMF). Partition coefficients were determined using 2-octanol as the organic phase and PBS solution as the aqueous phase. Fluorescence quantum yields ranged from 0.01 to 0.18 for all compounds, with heteroaryl porphyrins having the lowest values. Singlet oxygen quantum yields ranged from 0.40 to 0.65, with heteroaryl porphyrins having the highest values, showing them to be better sensitizers than m- and p-THPP. Log P values were all >1 showing higher solubility in the 2-octanol layer.
- Ormond, Alexandra B.,Freeman, Harold S.
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p. 440 - 448
(2013/02/23)
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- USE OF METALLOPORPHYRINS AND SALEN COMPLEXES FOR THE CATALYTIC OXIDATION OF ORGANIC COMPOUNDS
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A method of decomposing an organic substrate includes identifying an organic substrate or its constituents having one or more desired or undesired properties; and contacting the organic substrate with an oxidizing agent and a catalyst selected from the group consisting of sterically hindered and electronically activated metallotetraphenylporphyrms, metallophthalocyanines and metallosalen complexes in an aqueous or aqueous-organic solution to produce a treated composition comprising one or more degradation products, wherein the degradation products have one or more desired properties and/or lack the undesired properties of the organic substrate.
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Paragraph 0122
(2013/08/28)
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- Method Of Mass Production Of Tetrakis(P-Nitrophenyl)Porphyrins
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A method of mass production of tetrakis(p-nitrophenyl)porphyrins, by which successful isolation of the barely soluble product from meso-aryl nitration of tetraphenylporphyrin toward a remarkable yield of nearly 90% has been realized by means of a solid ph
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Paragraph 0017
(2013/07/31)
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- La(OTf)3-catalyzed one-pot synthesis of meso-substituted porphyrinic thiazolidinones
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An improved synthetic procedure is developed for the regioselective nitration of a phenyl group of meso-tetraphenylporphyrin by using NaNO 2 in a mixture of trichloroacetic acid and AcOH. The meso-(4-nitro-phenyl)porphyrins are successfully reduced to corresponding meso-(4-aminophenyl)porphyrins by SnCl2 under acidic conditions. In addition, an efficient one-pot methodology for synthesizing a series of novel meso-substituted porphyrinic thiazolidinone conjugates is developed by reacting meso-(4-aminophenyl)porphyrins with various aromatic aldehydes and mercaptoacetic acid in refluxing toluene using La(OTf)3 as a catalyst. The products obtained are characterized on the basis of their spectral data. Preliminary photophysical properties of the newly synthesized compounds are reported.
- Bhatt, Ranjan K.,Sharma, Satyasheel,Nath, Mahendra
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body text
p. 309 - 316
(2012/07/03)
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- Cobaltoporphyrin-catalyzed CO2/epoxide copolymerization: Selectivity control by molecular design
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A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures.
- Anderson, Carly E.,Vagin, Sergei I.,Xia, Wei,Jin, Hanpeng,Rieger, Bernhard
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p. 6840 - 6849,10
(2020/08/24)
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- Synthesis and properties of 5,10,15,20-tetrakis[4-(3,5-dioctyloxybenzamido) phenyl]porphyrin and its metal complexes
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A novel 5,10,15,20-tetrakis[4-(3,5-dioctyloxybenzamido)phenyl]-porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis as well as IR, 1H-NMR and UV-Vis spectroscopy. Their spectroscopic properties were studied by Raman and fluorescence spectroscopy, and X-ray photoelectron spectroscopy (XPS). The fluorescence quantum yields were measured at room temperature. The fluorescence intensity of the porphyrin ligand was stronger than the intensity of the complexes. There were large differences in the Raman spectrum of the porphyrin ligand and those of the metal complexes due to changes in the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin not only increases the symmetry of the molecule, but also introduces an electron withdrawing group into the center of the porphyrin ligand, which increases the N1S binding energy.
- Lian, Wenhui,Sun, Yuanyuan,Wang, Binbin,Shan, Ning,Shi, Tongshun
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scheme or table
p. 335 - 348
(2012/05/20)
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- Synthesis, characterization and spectral properties of substituted tetraphenylporphyrin iron chloride complexes
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A series of substituted tetraphenylporphyrin iron chloride complexes [RTPPFe(III)Cl, R=o/p-NO2, o/p-Cl, H, o/p-CH3, o/p-OCH3] were synthesized by a novel universal mixed-solvent method and the spectral properties of free b
- Sun, Zhi-Cheng,She, Yuan-Bin,Zhou, Yang,Song, Xu-Feng,Li, Kai
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scheme or table
p. 2960 - 2970
(2011/06/21)
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