- Efficient routes to A3B-type meso -(4-Carboxyphenyl) porphyrin derivatives
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A3B-type meso-(4-carboxyphenyl) porphyrins were prepared either by stepwise coupling of aniline substituents to meso-tetrakis(4-carboxyphenyl) porphyrin (TCPP) or by utilizing its partially protected trimethyl ester derivative. We demonstrate t
- Presolski, Stanislav I.,Van Der Weegen, Rob,Wiesfeld, Jan J.,Meijer
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- Coupling of a new porphyrin photosensitizer and cobaloxime cocatalyst for highly efficient photocatalytic H2evolution
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Photocatalytic hydrogen evolution (PHE) is a promising strategy to produce environmentally friendly clean energy with the use of solar power and water. For this, developing an efficient and noble metal free photocatalytic system (PS) comprising high light
- Bodedla, Govardhana Babu,Wong, Wai-Yeung,Zhu, Xunjin
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- H2S-Activable MOF Nanoparticle Photosensitizer for Effective Photodynamic Therapy against Cancer with Controllable Singlet-Oxygen Release
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Photodynamic therapy (PDT) has emerged as an important minimally invasive tumor treatment technology. The search for an effective photosensitizer to realize selective cancer treatment has become one of the major foci in recent developments of PDT technolo
- Ma, Yu,Li, Xiangyuan,Li, Aijie,Yang, Peng,Zhang, Caiyun,Tang, Bo
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- Ultrasonic assisted fabrication of dual function surface on PET and preparation of single component ink to attain efficient self-cleaning function via digital printing
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The self-cleaning effects of polyethylene terephthalate fabric (PET) through the photocatalytic effects of TiO2 (T), porphyrin (P) and silane (S) have been explored ultrasonically using bath type (WUC-D22H, Daihan Scientific, Korea). The ultras
- Manivannan, Ramalingam,Ryu, Jiwon,Son, Young-A
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- Towards synthetic-porphyrin/monoclonal antibody conjugates
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The synthesis of an unsymmetrically meso-aminoalkoxyphenyl-substituted porphyrin, and its conjugation to a monoclonal antibody (mAb), are described.
- Milgrom, Lionel R.,O'Neill, Faye
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- Two novel tcpp porphyrinic compounds: In situ syntheses, characterization and reaction mechanism
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Two novel porphyrinic compounds, {Zn[TCPP(CH2CH3)2(CH3)2]}n (1) and TCPP(CH3)4 (2) (TCPP = meso-Tetra(4-carboxyphenyl)porphyrin), with the TCPP(CH2CH3
- Zhang, Ding-Wa,Chen, Wen-Tong
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- Triplet–Triplet Annihilation Upconversion in a MOF with Acceptor-Filled Channels
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Photon upconversion has enjoyed increased interest in the last years due to its high potential for solar-energy harvesting and bioimaging. A challenge for triplet–triplet annihilation upconversion (TTA-UC) processes is to realize these features in solid materials without undesired phase segregation and detrimental dye aggregation. To achieve this, we combine a palladium porphyrin sensitizer and a 9,10-diphenylanthracene annihilator within a crystalline mesoporous metal–organic framework using an inverted design. In this modular TTA system, the framework walls constitute the fixed sensitizer, while caprylic acid coats the channels providing a solventlike environment for the mobile annihilator in the channels. The resulting solid material shows green-to-blue delayed upconverted emission with a luminescence lifetime of 373±5 μs, a threshold value of 329 mW cm?2 and a triplet–triplet energy transfer efficiency of 82 %. The versatile design allows straightforward changing of the acceptor amount and type.
- Gharaati, Shadab,Wang, Cui,F?rster, Christoph,Weigert, Florian,Resch-Genger, Ute,Heinze, Katja
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- Zirconium-metalloporphyrin PCN-222: Mesoporous metal-organic frameworks with ultrahigh stability as biomimetic catalysts
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Biomimetic MOF: Extremely stable MOFs with different open metal sites and ultra-large 1D channels, PCN-222 (Fe, Mn, Co, Ni, Cu, and Zn), have been assembled with eight-connected Zr6 clusters and redox-active metalloporphyrin motifs. PCN-222(Fe) shows peroxidase-like activity in aqueous solution, exhibiting highly effective biomimetic oxidation on a number of substrates. Copyright
- Feng, Dawei,Gu, Zhi-Yuan,Li, Jian-Rong,Jiang, Hai-Long,Wei, Zhangwen,Zhou, Hong-Cai
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p. 10307 - 10310,4
(2012)
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- Chlorin-Based Nanoscale Metal-Organic Framework Systemically Rejects Colorectal Cancers via Synergistic Photodynamic Therapy and Checkpoint Blockade Immunotherapy
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Photodynamic therapy (PDT) can destroy local tumors and minimize normal tissue damage, but is ineffective at eliminating metastases. Checkpoint blockade immunotherapy has enjoyed recent success in the clinic, but only elicits limited rates of systemic ant
- Lu, Kuangda,He, Chunbai,Guo, Nining,Chan, Christina,Ni, Kaiyuan,Weichselbaum, Ralph R.,Lin, Wenbin
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- Spectroscopy of protonated tetraphenylporphyrins with amino/carbomethoxy substituents: Hyperporphyrin effects and evidence for a monoprotonated porphyrin
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Spectrophotometric titrations for a full series of para-amino/carbomethoxy- substituted tetraphenylporphyrins were carried out using methanesulfonic acid in DMSO to study the hyperporphyrin effect across different substitution patterns. The series included zero, one, two (cis and trans), three, and four amino groups, with the remaining para substituents carbomethoxy groups. With increasing numbers of aminophenyl groups, the relative basicity increased and the hyperporphyrin effect increased, marked by a strong red band and a split Soret band. The cis diamino derivative showed a stronger hyperporphyrin effect compared to the trans isomer, which can be explained based on simple resonance forms. For the monoamino derivative, an initial increase in the Soret band upon acid titration along with well-defined isosbestic points provided evidence for a monoprotonated porphyrin, distinct from the diprotonated and triprotonated states. The relative stability of this unusual intermediate is proposed to be due to charge delocalization of the first cation to the single amino group and destabilization of the second protonation by the electron-withdrawing carbomethoxy substituents.
- Rudine, Alexander B.,Delfatti, Brian D.,Wamser, Carl C.
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- Boosting selective oxidation of cyclohexane over a metal-organic framework by hydrophobicity engineering of pore walls
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A porphyrinic metal-organic framework (MOF), PCN-222(Fe), was found to exhibit sound activity and selectivity to cyclohexanone and cyclohexanol (known as KA oil) toward cyclohexane oxidation. Remarkably, hydrophobicity engineering of the MOF pore walls le
- Li, Luyan,Yang, Qihao,Chen, Si,Hou, Xudong,Liu, Bo,Lu, Junling,Jiang, Hai-Long
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- Design and Synthesis of Supramolecular Polymer Network Equipped with Pd-porphyrin: An Efficient and Recoverable Heterogeneous Catalyst for C–C Coupling Reactions
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Abstract: The present study aimed to explain a modern and attractive protocol for synthesizing hypercross-linked conjugated supramolecular polymer network contains palladium(II) porphyrin based on calix[4]resorcinarene as an efficient heterogeneous cataly
- Hamid, Sheida,Mouradzadegun, Arash
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- NMR Spectra of the Porphyrins Part 39. Paramagnetic Shifts in Cobalt(II) Porphyrins
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A model of the paramagnetism in cobalt(II) porphyrin complexes has been developed which successfully calculates paramagnetic shifts for protons not affected by the contact term.The model utilizes a single large dipole positioned on the cobalt(II) atom, an
- Abraham, Raymond J.,Marsden, Ian,Xiujing, Lucy
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- A highly stable porphyrinic zirconium metal-organic framework with shp-a topology
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Through a kinetically controlled synthetic process, we synthesized PCN-223, a new porphyrinic Zr-MOF constructed from the newly reported hexagonal prismatic 12-connected Zr6 cluster through an unusual disordered arrangement, giving rise to the first example of the shp-a network in MOFs. With its extremely high connectivity, PCN-223 shows high stability in aqueous solutions with a wide range of pH. Cationic PCN-223(Fe) formed by postsynthetic treatment is an excellent recyclable heterogeneous catalyst for the hetero-Diels-Alder reaction.
- Feng, Dawei,Gu, Zhi-Yuan,Chen, Ying-Pin,Park, Jihye,Wei, Zhangwen,Sun, Yujia,Bosch, Mathieu,Yuan, Shuai,Zhou, Hong-Cai
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- Dye-sensitized solar cells using supramolecular porphyrin arrays inspired by π-stacking structures of photosynthetic light-harvesting complexes
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A slipped cofacial π-stacks of bis(4-carboxyphenyl)bis(1- methylimidazol-2-yl)porphyrinatomagnesium complex can be self-assembled onto TiO2 surface as a light-harvesting core. The porphyrin array allows a more favorable light-to-electricity conversion compared to the monomer analogue in dye-sensitized solar cells.
- Fujimoto, Junko,Manseki, Kazuhiro,Miyaji, Hidekazu
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- Metallization-Prompted Robust Porphyrin-Based Hydrogen-Bonded Organic Frameworks for Photocatalytic CO2 Reduction
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Under topological guidance, the self-assembly process based on a tetratopic porphyrin synthon results in a hydrogen-bonded organic framework (HOF) with the predicted square layers topology (sql) but unsatisfied stability. Strikingly, simply introducing a transition metal in the porphyrin center does not change the network topology but drastically causes noticeable change on noncovalent interaction, orbital overlap, and molecular geometry, therefore ultimately giving rise to a series of metalloporphyrinic HOFs with high surface area, and excellent stability (intact after being soaked in boiling water, concentrated HCl, and heated to 270 °C). On integrating both photosensitizers and catalytic sites into robust backbones, this series of HOFs can effectively catalyze the photoreduction of CO2 to CO, and their catalytic performances greatly depend on the chelated metal species in the porphyrin centers. This work enriches the library of stable functional HOFs and expands their applications in photocatalytic CO2 reduction.
- Alexandrov, Eugeny V.,Fang, Zhi-Bin,Huang, Qian-Qian,Li, Yu-Lin,Liu, Tian-Fu,Proserpio, Davide M.,Qin, Wei-Kang,Si, Duan-Hui,Yin, Qi,Zhang, An-An,Zhang, Yuan
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supporting information
(2021/12/24)
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- The effect of aromatic and non-aromatic ionic liquids on the optical nonlinearity responses of porphyrins
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The effects of adding aromatic and nonaromatic ionic liquids (ILs) on third-order nonlinear optical (NLO) responses of 5,10,15,20-Tetrakis(4-methoxycarbonylphenyl) porphyrin (S1) and [5,10,15,20-Tetrakis(4-methoxycarbonylphenyl)-porphyrin]–Co (II) (S2) at
- Ahmadi, Vahid Jan,Nadafan, Marzieh,Sabbaghan, Maryam
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- Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches
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Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi-homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene-based photoswitches. The facile sepa
- Lorenz, Patrick,Luchs, Tobias,Hirsch, Andreas
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supporting information
p. 4993 - 5002
(2021/02/26)
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- Straightforward synthesis of a porous chromium-based porphyrinic metal-organic framework for visible-light triggered selective aerobic oxidation of benzyl alcohol to benzaldehyde
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Among MOFs, chromium-based metal–organic frameworks (Cr-MOFs) represent attractive scaffolds for variety of potential applications due to their high porosity and stability. Nevertheless, Cr-MOFs are not very common due to complicate synthesis. Cr-MOFs of large linkers are one clear example of synthetic limitations, since their preparation takes place by post-synthetic routes, commonly starting from Fe-MOFs as precursors. Hence, in this work, the direct synthesis of a phorphyrinic chromium-based MOF, Cr-PCN-600 (PCN stands for Porous Coordination Network) under solvothermal conditions is reported. The resulting Cr-MOF exhibits high surface area, permanent porosity, and broad light absorption wavelength range. Interestingly, this Cr-MOF is a highly effective heterogeneous photocatalyst for the selective aerobic oxidation of benzyl alcohol to benzaldehyde under visible light irradiation without any additive. Importantly, the Cr-MOF showed good recyclability maintaining its activity for three runs. The present results lay the foundation for both synthesis and applications of Cr-MOFs as robust photocatalysts in advanced organic transformations. Notably, quenching studies confirmed the generation of superoxide radical anion (O2[rad]?) and singlet oxygen (1O2) (mostly) as reactive species under the reaction conditions.
- Daliran, Saba,García, Hermenegildo,Khajeh, Mostafa,Luque, Rafael,Oudi, Sara,Oveisi, Ali Reza,Sen, Unal
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- Porphyrin-based NiFe Porous Organic Polymer Catalysts for the Oxygen Evolution Reaction
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Porphyrin-based NiFe porous organic polymers (POPs) have been synthesized with good porosity and large BET surface areas (261 to 313 m2 g?1). These bimetallic POPs exhibit RuO2-like OER activity, with the reaction for catalyst FeTAPP-NiTCPP-POP reaching a current density of 10 mA cm?2 at a low overpotential of 338 mV and with a small Tafel slope of 52 mV dec?1. FeTAPP-NiTCPP-POP was stable over a long period under reaction conditions. These bimetallic POPs exhibit better catalytic activity than their monometallic counterparts, due to synergetic interactions between the iron and nickel centers to facilitate the electrocatalytic process.
- Meng, Jing,Xu, Ze,Li, Hongxi,James Young, David,Hu, Chuanjiang,Yang, Yonggang
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p. 1396 - 1402
(2021/02/03)
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- Immobilization of Rh(i) precursor in a porphyrin metal-organic framework - turning on the catalytic activity
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Two model porphyrin metal-organic frameworks were used for the incorporation of Rh(i) species by a post-synthetic metallation under mild conditions. As a result, new rhodium MOFs (Rh/MOFs),Rh/PCN-222andRh/NU-1102, were synthesized and structurally characterized. To illustrate the potential of this catalytic platform, we use Rh/MOFs as phosphine-free heterogeneous catalysts in the hydrogenation of unsaturated hydrocarbons under mild reaction conditions (30 °C and 1 atm H2). We found that for our Rh/MOFs an activation step is required during the first run of the catalytic process. The presence of Rh-CO moieties allowed us to monitor the activation pathway of the catalyst under a H2atmosphere, byin situDiffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). After activation, the catalyst remains highly active during the subsequent catalytic cycles. This simple post-synthetic modification approach presents new possibilities for the utilization of Rh-based catalytic systems with robust porphyrin-based MOFs as supports.
- Bury, Wojciech,Janeta, Mateusz,Siczek, Mi?osz,Szczepkowska, Anna M.,Trzeciak, Anna M.,Tylus, W?odzimierz
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supporting information
p. 9051 - 9058
(2021/07/12)
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- Porphyrin-Based Metal-Organic Frameworks for Efficient Photocatalytic H2Production under Visible-Light Irradiation
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Metal-organic frameworks (MOFs) are important photocatalytic materials for H2 production. To clarify the structure-function relationship and improve the photocatalytic activity, herein we explored a series of porphyrin-based zirconium MOFs (PCN-H2/Ptx:y, where x:y = 4:1, 3:2, 2:3, and 0:1) containing different ratios of H2TCPP and PtIITCPP [TCPP = tetrakis(4-carboxyphenyl)porphyrinate] as isostructural ligands and Zr6 clusters as nodes. Under visible-light irradiation, PCN-H2/Pt0:1 shows the highest average H2 evolution reaction rate (351.08 μmol h-1 g-1), which decreases along with lowering of the ratio of PtIITCPP in the PCN-H2/Ptx:y series. The differences in photocatalytic activity are attributed to more uniformly dispersed Pt2+ ions in PCN-H2/Pt0:1, which promotes charge transfer from porphyrins (photosensitizers) to PtII ions (catalytic centers), leading to efficient charge separation in the MOF materials. The bifunctional MOFs with photosensitizers and catalytic centers provide new insight for the design and application of porphyrin-based photocatalytic systems for visible-light-driven H2 production.
- Lin, Chenxiang,Han, Chaozheng,Zhang, Haijiao,Gong, Lei,Gao, Ying,Wang, Hailong,Bian, Yongzhong,Li, Renjie,Jiang, Jianzhuang
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supporting information
p. 3988 - 3995
(2021/04/07)
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- Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
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The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
- Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
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- Manganese porphyrin-based metal-organic framework for synergistic sonodynamic therapy and ferroptosis in hypoxic tumors
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Development of efficient therapeutic strategy to incorporate ultrasound (US)-triggered sonodynamic therapy (SDT) and ferroptosis is highly promising in cancer therapy. However, the SDT efficacy is severely limited by the hypoxia and high glutathione (GSH) in the tumor microenvironment, and ferroptosis is highly associated with reactive oxygen species (ROS) and GSH depletion. Methods: A manganese porphyrin-based metal-organic framework (Mn-MOF) was constructed as a nanosensitizer to self-supply oxygen (O2) and decrease GSH for enhanced SDT and ferroptosis. In vitro and in vivo analysis, including characterization, O2 generation, GSH depletion, ROS generation, lipid peroxidation, antitumor efficacy and tumor immune microenvironment were systematically evaluated. Results: Mn-MOF exhibited catalase-like and GSH decreasing activity in vitro. After efficient internalization into cancer cells, Mn-MOF persistently catalyzed tumor-overexpressed H2O2 to in-situ produce O2 to relieve tumor hypoxia and decrease GSH and GPX4, which facilitated the formation of ROS and ferroptosis to kill cancer cells upon US irradiation in hypoxic tumors. Thus, strong anticancer and anti-metastatic activity was found in H22 and 4T1 tumor-bearing mice after a single administration of Mn-MOF upon a single US irradiation. In addition, Mn-MOF showed strong antitumor immunity and improved immunosuppressive microenvironment upon US irradiation by increasing the numbers of activated CD8+ T cells and matured dendritic cells and decreaing the numbers of myeloid-derived suppressor cells in tumor tissues. Conclusions: Mn-MOF holds great potential for hypoxic cancer therapy.
- Xu, Qingbo,Zhan, Guiting,Zhang, Zelong,Yong, Tuying,Yang, Xiangliang,Gan, Lu
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p. 1937 - 1952
(2021/01/06)
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- Defect-engineered porphyrinic metal-organic framework nanoparticles for targeted multimodal cancer phototheranostics
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Defect-engineered porphyrinic MOF nanoparticles were fabricated with anin situone-pot protocol using cypate as the co-ligand and modulator. This multifunctional nanoplatform integrated the photothermal and multimodal imaging properties of cypate with the photodynamic effects of porphyrins, thus achieving targeted multimodal cancer phototheranostics after folic acid modification.
- Wang, Chenyuan,Xiong, Chuxiao,Li, Zhike,Hu, Liefeng,Wei, Jianshuang,Tian, Jian
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supporting information
p. 4035 - 4038
(2021/04/28)
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- Porphyrinic MOF Film for Multifaceted Electrochemical Sensing
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Electrochemical sensors are indispensable in clinical diagnosis, biochemical detection and environmental monitoring, thanks to their ability to detect analytes in real-time with direct electronic readout. However, electrochemical sensors are challenged by sensitivity—the need to detect low concentrations, and selectivity—to detect specific analytes in multicomponent systems. Herein, a porphyrinic metal-organic framework (PP-MOF), Mn-PCN-222 is deposited on a conductive indium tin oxide (ITO) surface. It affords Mn-PCN-222/ITO, a versatile voltammetric sensor able to detect redox-active analytes such as inorganic ions, organic hazardous substances and pollutants, including nitroaromatics, phenolic and quinone-hydroquinone toxins, heavy metal ions, biological species, as well as azo dyes. As a working electrode, the high surface area of Mn-PCN-222/ITO enables high currents, and therefore leverages highly sensitive analysis. The metalloporphyrin centre facilitates analyte-specific redox catalysis to simultaneously detect more than one analyte in binary and ternary systems allowing for detection of a wide array of trace pollutants under real-world conditions, most with high sensitivity.
- Elsner, Martin,Fischer, Roland A.,Hou, Shujin,Li, Weijin,Mukherjee, Soumya,Zhou, Zhenyu
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supporting information
p. 20551 - 20557
(2021/08/09)
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- Efficient and selective oxidation of 5-hydroxymethylfurfural catalyzed by metal porphyrin supported by alkaline lignin: Solvent optimization and catalyst loading
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Cobalt (II)-meso-tetra(4-carboxyphenyl) porphyrin supported by deprotected lignin was synthesized through the covalent linkage between carboxy groups in the porphyrin and hydroxyl groups in the lignin. The resulting supporting catalysts were applied in the selective oxidation of 5-hydroxymethylfurfural. Through solvent optimization, 5-hydroxymethyl-2-furancarboxylic acid and 2,5-furandicarboxylic acid could be selectively obtained. Steric effect of lignin prevented unwanted aggregation-caused quenching, avoiding catalyst deactivation. Thus, supported catalysts displayed better catalytic efficiency compared free metal porphyrin catalyst. Unlike the excessive use of sodium hydroxide in the oxidation of HMF catalyzed by metal catalysts, an equivalent amount of sodium hydroxide was used in this oxidation process. Meanwhile, lower activation energy was detected when metal porphyrin supported by deprotected lignin was used. By adjusting the pH in the reaction, supported catalysts could be reused. The catalytic activity remained stable during the recycling experiments.
- Fang, Zheng,Guo, Kai,He, Wei,Wu, Hao,Yang, Xiaobing,Zhu, Yuchen
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- Carboxyl functionalized platinum porphyrin material as well as preparation method and application thereof
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The invention relates to the technical field of catalytic materials, and discloses a carboxyl functionalized platinum porphyrin material as well as a preparation method and application thereof. The material is obtained 5, 10, 15, 20 - (substituted methyl
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Paragraph 0064-0065; 0068-0069; 0072-0073
(2021/11/03)
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- Investigation of antimony adsorption on a zirconium-porphyrin-based metal-organic framework
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A zirconium-porphyrin based organic framework PCN-222 was employed for investigating the adsorption performance of Sb(iii) in aqueous solution. It is proved that the adsorbent has the advantages of rapid adsorption and high capacity. Interestingly, we discover that PCN-222 shows pH-dependent adsorption performance, with higher capacity at pH = 2 and 8 than at pH = 5. According to XPS and FT-IR analyses, an adsorption model of PCN-222 with pH = 2, 5, and 8 is proposed, that is, zirconium clusters combine with antimony at different pH values with bidentate complexes, monodentate complexes, and alkaline monodentate complexes, thus producing an excellent adsorption effect. Moreover, the porphyrin ring is also beneficial for the adsorption of antimony. In addition, PCN-222 shows good regeneration and recycling performance, and it is a promising adsorbent as well as a platform for investigating the removal of Sb(iii) in water treatment.
- Guo, Rongxiu,Guo, Ying,Jia, Hongna,Li, Hong,Niu, Dun,Sun, Hong-Bin,Sun, Zejun,Wang, Yao,Xie, Nianyi,Zhang, Xinyue
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p. 13932 - 13942
(2021/10/19)
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- Symmetry-Guided Synthesis of N,N′-Bicarbazole and Porphyrin-Based Mixed-Ligand Metal-Organic Frameworks: Light Harvesting and Energy Transfer
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In the past decades, many attempts have been made to mimic the energy transfer (EnT) in photosynthesis, a key process occurring in nature that is of fundamental significance in solar fuels and sustainable energy. Metal-organic frameworks (MOFs), an emerging class of porous crystalline materials self-assembled from organic linkers and metal or metal cluster nodes, offer an ideal platform for the exploration of directional EnT phenomena. However, placing energy donor and acceptor moieties within the same framework with an atomistic precision appears to be a major synthesis challenge. In this work, we report the design and synthesis of a highly porous and photoactive N,N′-bicarbazole- and porphyrin-based mixed-ligand MOF, namely, NPF-500-H2TCPP (NPF = Nebraska porous framework; H2TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin), where the secondary ligand H2TCPP is incorporated precisely through the open metal sites of the equatorial plane of the octahedron cage resulting from the underlying (4,8) connected network of NPF-500. The efficient EnT process from N,N′-bicarbazole to porphyrin in NPF-500-H2TCPP was captured by time-resolved spectroscopy and exemplified by photocatalytic oxidation of thioanisole. These results demonstrate not only the capability of NPF-500 as the scaffold to precisely arrange the donor-acceptor assembly for the EnT process but also the potential to directly utilize the EnT process for photocatalytic applications.
- Fiankor, Christian,Hu, Yuchen,Huang, Jier,Khoo, Rebecca Shu Hui,Nyakuchena, James,Yang, Sizhuo,Zhang, Jian,Zhang, Xu
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supporting information
p. 20411 - 20418
(2021/12/03)
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- A series of asymmetric and symmetric porphyrin derivatives: one-pot synthesis, nonlinear optical and optical limiting properties
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In this work, a series of asymmetric and symmetric porphyrin derivatives (structure types: A4, A3B1,trans-A2B2,cis-A2B2, A1B3, and B4) have been synthesizedviaa one-pot method and characterized by TLC, HPLC, FT-IR,1H-NMR and UV-Vis to identify their structures and properties. The porphyrin derivatives withtrans-A2B2andcis-A2B2structures are visually distinguishedviasingle-crystal X-ray diffraction; the crystal morphology oftrans-A2B2is a needle-like structure. All porphyrin derivatives (I-VI) have excellent nonlinear optical (NLO) and optical limiting (OL) properties, and are investigated using the standardZ-scan technique. Porphyrin derivativeIIIexhibits the maximum nonlinear absorption, nonlinear refraction coefficients and optical limitation threshold, and the values are 3.7 × 10?9m W?1, ?17 × 10?17m2W?1and 0.11 J cm?2, respectively. The results demonstrate that the introduction of different substituent numbers (mono-, di- and tri-, tetra-) and substituent sites (trans-A2B2andcis-A2B2) in the porphyrins could influence the NLO and OL properties. Structure regulation of porphyrin can lead to the adjustment of NLO and OL properties, and affect its practical NLO application in the future.
- Bao, Changjiang,Chen, Changshun,Duan, Qian,Li, Yanhui,Li, Yanwei,Si, Zhenjun,Wang, Lei,Zhang, Yanru
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p. 16030 - 16038
(2021/09/22)
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- Pd-porphyrin complex-catalyzed allylation of indole with allylic alcohols through C3–C2 coupling
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Appropriate and efficient way for the preparation of 3-allyl-2,3-dihydro-2,3′-bisindoles has been developed via homocoupling of N–H indole. Pd-porphyrin-catalyzed allylation of indoles with allylic alcohols in the presence of PBr3 and a base is developed. The reaction involves dimerization at the C3 and C2 positions of the indoles, giving 2-allylated 3-(indolin-2-yl)-1H-indoles in moderate to good yields. 3-(Indolin-2-yl)-1H-indole derivatives serve as intermediates for the synthesis of pharmaceutically active molecules.
- Atia, Alaa A.,Kimura, Masanari
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supporting information
(2021/05/19)
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- Modulating the Acidic and Basic Site Concentration of Metal-Organic Framework Derivatives to Promote the Carbon Dioxide Epoxidation Reaction
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Metal-organic framework (MOF) is an ideal precursor/template for porous carbon, and its active components are uniformly doped, which can be used in energy storage and catalytic conversion fields. Metal-organic framework PCN-224 with carboxylporphyrin as t
- Ji, Jinhua,Liu, Hao,Chen, Zewei,Fu, Yajun,Yang, Weijun,Yin, Shuang-Feng
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p. 11102 - 11109
(2021/06/25)
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- Metalloporphyrin supported on hyper cross-linked polymer: green protocol for reduction of nitroarenes
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In the current study, a Pd–porphyrin catalyst was anchored covalently onto functionalized polymeric spine based on a calix[4]resorcinarene. The achieved catalytic system was characterized, and its catalytic activity was investigated in the reduction of nitroarenes. The main advantages of the present work are: using water as green solvent, catalyst reusability, easy refinement of the products, excellent yields, and relatively short reaction times.
- Hamid, Sheida,Mouradzadegun, Arash
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p. 213 - 221
(2020/08/24)
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- Titanium Metal-Organic Framework Single Crystal
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A titanium metal-organic framework (Ti MOF) single crystal according to the present invention includes a titanium-oxo structural unit, wherein a tetravalent organic ligand that absorbs visible light is bound to titanium of the titanium-oxo structural unit, and four functional groups of the tetravalent organic ligand are bound to different titanium, separately. The Ti MOF single crystal according to the present invention has low band gap energy, excellent microporosity and high specific surface area.COPYRIGHT KIPO 2020
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Paragraph 0118-0110
(2020/07/11)
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- A Porphyrinic Zirconium Metal-Organic Framework for Oxygen Reduction Reaction: Tailoring the Spacing between Active-Sites through Chain-Based Inorganic Building Units
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The oxygen reduction reaction (ORR) is central in carbon-neutral energy devices. While platinum group materials have shown high activities for ORR, their practical uses are hampered by concerns over deactivation, slow kinetics, exorbitant cost, and scarce
- Cichocka, Magdalena Ola,Liang, Zuozhong,Feng, Dawei,Back, Seoin,Siahrostami, Samira,Wang, Xia,Samperisi, Laura,Sun, Yujia,Xu, Hongyi,Hedin, Niklas,Zheng, Haoquan,Zou, Xiaodong,Zhou, Hong-Cai,Huang, Zhehao
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supporting information
p. 15386 - 15395
(2020/10/20)
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- Multi-component supramolecular gels induce protonation of a porphyrin exciplex to achieve improved collective optical properties for effective photocatalytic hydrogen generation
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Towards mimicking natural photosystems, supramolecular gels containing two types of porphyrins were developed for photocatalysis. Protonation and J-aggregation of porphyrins within gels expand the absorption to a wide range of visible wavelengths. Porphyrin exciplex formation renders a smaller bandgap for photo-induced electron generation. These features induce effective photocatalytic hydrogen generation.
- Feng, Xuenan,Jiang, Jianzhuang,Lin, Chenxiang,Wang, Tianyu,Yang, Gengxiang
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supporting information
p. 527 - 530
(2020/01/29)
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- Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis
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Discoveries of the accurate spatial arrangement of active sites in biological systems and cooperation between them for high catalytic efficiency are two major events in biology. However, precise tuning of these aspects is largely missing in the design of artificial catalysts. Here, a series of metal–organic frameworks (MOFs) were used, not only to overcome the limit of distance between active sites in bio-systems, but also to unveil the critical role of this distance for efficient catalysis. A linear correlation was established between photocatalytic activity and the reciprocal of inter active-site distance; a smaller distance led to higher activity. Vacancies created at selected crystallographic positions of MOFs promoted their photocatalytic efficiency. MOF-525-J33 with 15.6 ? inter active-site distance and 33 % vacancies exhibited unprecedented high turnover frequency of 29.5 h?1 in visible-light-driven acceptorless dehydrogenation of tetrahydroquinoline at room temperature.
- Deng, Hexiang,Gong, Xuan,Jiang, Zhuo,Lu, Lingxiang,Shu, Yufei,Wang, Chao,Xu, Xiaohui
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supporting information
p. 5326 - 5331
(2020/02/18)
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- In situ self-assembly of zirconium metal-organic frameworks onto ultrathin carbon nitride for enhanced visible light-driven conversion of CO2 to CO
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A series of Zr-porphyrin metal-organic framework (Zr-PMOF)/ultrathin g-C3N4 (UCN) (ZPUCN) heterostructure photocatalysts, as stable and efficient catalysts for the photoreduction of CO2, have been fabricated via a facile in situ hydrothermal self-assembly method. An interfacial interaction is formed due to hollow Zr-PMOF nanotubes being surrounded by 3D ultrathin g-C3N4 (UCN) and benefiting from the ultrathin and conjugated π-structure of UCN, the unsaturated metal atoms and organic ligands of Zr-PMOFs can covalently link to organic g-C3N4. The interaction provides a platform for UCN as a conductor to transfer e- or as a donor to transfer e- to Zr-O cluster active sites to catalyze CO2, substantially achieving the spatial separation of charge carriers and suppressing the photogenerated electron-hole (e--h+) pair recombination rate. Benefitting from the cooperative effects of the well-designed nanostructure and chemical grafting, in the absence of triethanolamine, cocatalysts and photosensitizers, the optimized ZPUCN hybrid not only exhibits a better CO evolution yield (5.05 μmol g-1 h-1), which is 2.2 times and 3.2 times higher than those of pure Zr-PMOFs and UCN, respectively, but also displays excellent stability after 96 h photocatalysis. Information about the mechanism is also elucidated from selected characterizations.
- Guo, Haiwei,Wan, Shipeng,Wang, Yanan,Zeng, Yiqing,Zhang, Shule,Zhen, Wenlong,Zhong, Qin
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supporting information
p. 6034 - 6040
(2020/04/08)
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- A series of highly stable porphyrinic metal-organic frameworks based on iron-oxo chain clusters: design, synthesis and biomimetic catalysis
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Iron-based porphyrinic metal-organic frameworks (PMOFs) are desirable for biomimetic applications, due to the low toxicity and high abundance of Fe as well as the rich biomimetic functions of metalloporphyrins. Besides, the uniform dispersion of porphyrin centers in PMOFs can effectively protect them from self-dimerization. Nevertheless, it remains a big challenge to synthesize iron-based PMOFs. In this study, a series of Fe-oxo chain-based PMOFs incorporating different metals in porphyrinic centers (namely M-PMOF-3(Fe), M = Fe, Co, Ni, Cu) are synthesized directly from the reaction of metalloporphyrin and iron salts with an improved modulating strategy using a pair of monocarboxylic acids and water as the three-component modulator. The prepared materials of M-PMOF-3(Fe) possess high stability to resist a broad pH range (0-11) and even 2 M HCl in aqueous solutions for 2 days, and their frameworks can be maintained up to 350 °C. Catalytic tests show that M-PMOF-3(Fe) are effective in the aerobic oxidation of C-H bonds using oxygen from the air as the oxidant.
- Liu, Gang,Cui, Hao,Wang, Sujuan,Zhang, Li,Su, Cheng-Yong
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supporting information
p. 8376 - 8382
(2020/05/16)
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- Boosting Interfacial Charge-Transfer Kinetics for Efficient Overall CO2Photoreduction via Rational Design of Coordination Spheres on Metal-Organic Frameworks
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The recombination of electron-hole pairs severely detracts from the efficiency of photocatalysts. This issue could be addressed in metal-organic frameworks (MOFs) through optimization of the charge-transfer kinetics via rational design of structures at atomic level. Herein, a pyrazolyl porphyrinic Ni-MOF (PCN-601), integrating light harvesters, active catalytic sites, and high surface areas, has been demonstrated as a superior and durable photocatalyst for visible-light-driven overall CO2 reduction with H2O vapor at room temperature. Kinetic studies reveal that the robust coordination spheres of pyrazolyl groups and Ni-oxo clusters endow PCN-601 with proper energy band alignment and ultrafast ligand-to-node electron transfer. Consequently, the CO2-to-CH4 production rate of PCN-601 far exceeds those of the analogous MOFs based on carboxylate porphyrin and the classic Pt/CdS photocatalyst by more than 3- and 20-fold, respectively. The reaction avoids the use of hole scavengers and proceeds in a gaseous phase which can take full advantage of the high gas uptake of MOFs. This work demonstrates that the rational design of coordination spheres in MOF structures not only reconciles the contradiction between reactivity and stability but also greatly promotes the interfacial charge transfer to achieve optimized kinetics, providing guidance for the design of highly efficient MOF photocatalysts.
- Cao, Rong,Fang, Zhi-Bin,Gong, Xue-Qing,Jin, Shengye,Liu, Junxue,Liu, Tian-Fu,Liu, Ting-Ting,Wang, Kecheng,Wu, Xin-Ping,Yin, Qi,Zhou, Hong-Cai
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supporting information
p. 12515 - 12523
(2020/08/07)
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- Remote ion-pair interactions in Fe-porphyrin-based molecular catalysts for the hydrogen evolution reaction
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The environmentally benign production of clean energy is extremely important for the sustainable progress of our society. In this respect, dihydrogen (H2) has been considered in the last decades as an efficient energy carrier and much effort has been directed to the hydrogen evolution reaction (HER). Herein, we report on the efficiency of iron-based 5,10,15,20-tetraphenylporphyrins containing carboxylate groups in different positions (ortho, meta and para of the meso-substituted aryl groups of the porphyrin backbone) as molecular catalysts for the HER. The iron-based porphyrin containing the carboxylic acids in the ortho position was found completely inactive in the HER. Furthermore, besides stereoelectronic control, the subtle differences observed in the cyclic voltammograms (CV) as well as those associated with the electrocatalytic activity might involve a previously neglected ion-pair interaction between the carboxylate groups of the porphyrin scaffold and the chloride anions belonging to the proton source, which highlights the relevance of ion-pair contacts remote from the active center for this type of catalytic system.
- Kasemthaveechok, Sitthichok,Fabre, Bruno,Loget, Gabriel,Gramage-Doria, Rafael
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p. 1301 - 1308
(2019/03/12)
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- Single-Atom catalysts templated by metal-organic frameworks for electrochemical nitrogen reduction
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The electrocatalytic nitrogen reduction reaction (NRR) has much prospect for substituting the energy-consuming Haber-Bosch process. Nevertheless, its sluggish reaction kinetics and the competing hydrogen evolution reaction always result in limited ammonia yield and low faradaic efficiency (FE). In this work, an Fe-decorated porphyrinic metal-organic framework (MOF) is employed as a precursor to construct single-Atom Fe implanted nitrogen-doped carbon catalysts (Fe1-N-C) through a mixed ligand strategy. Benefiting from the highly dispersed single-Atom Fe sites, hierarchically porous structure and good conductivity, Fe1-N-C shows a FE of 4.51% and an ammonia yield rate of 1.56 × 10-11 mol cm-2 s-1 at-0.05 V versus the reversible hydrogen electrode, superior to those of Co1-N-C and Ni1-N-C. Theoretical calculations reveal that Fe1-N-C shows the lowest energy barrier of the rate-determining step during the NRR process, consistent with its highest activity obtained in experiments. This work reveals the unique potential of single-Atom catalysts for the electrochemical NRR and provides in-depth insights into the catalytic mechanism of the NRR.
- Zhang, Rui,Jiao, Long,Yang, Weijie,Wan, Gang,Jiang, Hai-Long
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p. 26371 - 26377
(2019/12/04)
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- Fluorescence lifetime imaging of upper gastrointestinal pH in vivo with a lanthanide based near-infrared τ probe
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Time-resolved fluorescence lifetime imaging (FLIM) in the near-infrared region of 900-1700 nm not only allows a deep tissue penetration depth but also offers the unique benefit of the quantitative visualization of molecular events in vivo and is independe
- Ning, Yingying,Cheng, Shengming,Wang, Jing-Xiang,Liu, Yi-Wei,Feng, Wei,Li, Fuyou,Zhang, Jun-Long
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p. 4227 - 4235
(2019/04/17)
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- Structural Transformation in Metal–Organic Frameworks for Reversible Binding of Oxygen
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Polycyclic aromatic derivatives can trap 1O2 to form endoperoxides (EPOs) for O2 storage and as sources of reactive oxygen species. However, these materials suffer from structural amorphism, which limit both practical applications and fundamental studies on their structural optimization for O2 capture and release. Metal–organic frameworks (MOFs) offer advantages in O2 binding, such as clear structure–performance relationships and precise controllability. Herein, we report the reversible binding of O2 is realized via the chemical transformation between anthracene-based and the corresponding EPO-based MOF. It is shown that anthracene-based MOF, the framework featuring linkers with polycyclic aromatic structure, can rapidly trap 1O2 to form EPOs and can be restored upon UV irradiation or heating to release O2. Furthermore, we confirm that photosensitizer-incorporated anthracene-based MOF are promising candidates for reversible O2 carriers controlled by switching Vis/UV irradiation.
- Zeng, Jin-Yue,Wang, Xiao-Shuang,Qi, Yong-Dan,Yu, Yun,Zeng, Xuan,Zhang, Xian-Zheng
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p. 5692 - 5696
(2019/03/27)
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- A simple strategy for engineering heterostructures of Au nanoparticle-loaded metal-organic framework nanosheets to achieve plasmon-enhanced photocatalytic CO2 conversion under visible light
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Carbon dioxide selectively concentrated in micropores of metal-organic frameworks (MOFs) and light absorption units as bridged ligands or guest molecules incorporated into MOF matrices are positive effects on upgrading reactivity of metal catalytic centers towards CO2 conversion through high-efficient quasi-intramolecular electron transfer among them. However, in contrast to the surfaces of MOFs, sluggish mass transfer of CO2, as well as of products, in micropores could negatively affect photocatalytic activity for CO2 reduction. Moreover, interactions between light and matter are heavily blocked if light absorption units are buried deep in bulky MOF matrices. In this research, hybrids of thin porphyrin paddle-wheel framework-3 (PPF-3) nanosheets (PPF-3-1) anchored with AuNPs are prepared by an electrostatic interaction to address these questions. This mainly involves improvement of PPF-3 morphology and the assembly mode between Au nanoparticles (AuNPs) and PPF-3 nanosheets. On the one hand, thin nanosheets can induce faster charge transfer rate and higher mass transport capability than thick nanosheets in the photocatalytic process; on the other hand, plasmonic AuNPs loaded onto the surfaces of nanosheets lead to more effective light absorption than AuNPs encapsulated in the matrices of nanosheets. Finally, the hybrids exhibit superior photocatalytic activity for CO2 conversion into HCOOH in an acetonitrile/ethanol system by plasmon resonance energy transfer process compared with pure PPF-3-1 or hybrids of thick PPF-3 nanosheets (PPF-3-2) supporting AuNPs. The research offers a novel and universal strategy to build high-efficiency MOF-based photocatalysts with enhanced performance for selective photocatalytic CO2 reduction.
- Chen, Liyong,Wang, Yanxin,Yu, Fengyang,Shen, Xiaoshuang,Duan, Chunying
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supporting information
p. 11355 - 11361
(2019/05/16)
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- A novel drug-drug nanohybrid for the self-delivery of porphyrin and: Cis-platinum
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The thriving development of nanotechnology has greatly promoted the development of drug delivery systems (DDSs) in the past decades. However, most DDSs themselves cannot serve as diagnostic reagents and must be metabolized, by which they may become poisonous and even cause immune reactions. In this study, a novel self-delivery drug-drug system (SDDS) nanohybrid based on the coordination assembly of a photodynamic reagent, tetra-(4-carboxyphenyl)porphyrin (TCPP), and a chemotherapy reagent, cis-platinum, was designed and synthesized. The four carboxyl groups of TCPP can compete with the chloride ions of cis-platinum by coordination interactions, forming a TCPP-cis-platinum nanohybrid (PCNH) for the purpose of photodynamic/chemotherapeutic synergistic treatment with a combinational index of 0.28. Meanwhile, the PCNH system can effectively protect the photosensitizer TCPP from photobleaching when irradiated continuously in the photodynamic therapy (PDT) process, which is very crucial for PDT. Furthermore, introduction of the heavy atom platinum can greatly enhance the producing efficiency of 1O2 by 46%. In addition, the red emission fluorescence of TCPP is beneficial for monitoring and tracing the process of drug delivery when used in vitro. This work may pave a new way for the design of new integrated nanohybrids for diagnosis and synergistic treatment.
- Shan, Changfu,Ru, Jiaxi,Zhang, Meina,Cao, Jing,Liu, Weisheng,Guo, Huichen,Tang, Yu
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p. 37003 - 37008
(2019/11/25)
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- A large π-conjugated tetrakis (4-carboxyphenyl) porphyrin anode enables high specific capacity and superior cycling stability in lithium-ion batteries
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We demonstrated a novel single molecule-tetrakis(4-carboxyphenyl) porphyrin (TCPP) with a large π-conjugated system as a high-performance organic anode of lithium batteries. It was found that this TCPP displayed relatively low solubility (-1) in a 1 M LiDFOB/PC electrolyte, high reversible specific capacity (ca. 1200 mA h g-1 at 358 mA g-1), excellent rate capability (548.4 mA h g-1 at 8 A g-1) and superior cycling performance (capacity retention of 89percent after 2500 cycles at 6 A g-1).
- Cui, Guanglei,Du, Xiaofan,Liu, Hao,Luo, Ting,Wu, Han,Xu, Hai,Yang, Jinfeng,Zhang, Jianjun,Zhang, Jinning,Zhang, Min
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supporting information
p. 11370 - 11373
(2019/09/30)
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- Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster
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Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3 m2 g?1) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen (1O2) and superoxide (.O2?) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.
- Keum, Yesub,Park, Seonghun,Chen, Ying-Pin,Park, Jinhee
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supporting information
p. 14852 - 14856
(2018/10/20)
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- A porphyrin cobalt(II) complex linked to a TiO2/BiVO4 nanocomposite: Alcohol oxidation using nanohybrid materials as a photocatalyst: Via a mechanism approach
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Herein, a new nanohybrid catalyst was synthesized via covalently linking a tetraacetate porphyrin cobalt(ii) complex to a TiO2/BiVO4 nanocomposite, and its photocatalytic efficiency towards alcohol oxidation under visible light irradiation was monitored by GC. This nanohybrid material was implemented as a photocatalyst and characterized by the following physicochemical techniques: FE-SEM imaging, EDS, XRD, DRS, BET analysis, and FTIR spectroscopy. Additionally, its role as a photocatalyst was evaluated using a mechanistic approach under aerobic conditions by changing several parameters such as solvent, substrate, oxidant, amount of catalyst, reaction temperature, and ratio of oxidant to substrate. The photocatalytic activity of this nanohybrid catalyst, with an average size of 24 nm, increased almost twice as compared to that of the TiO2/BiVO4 nanocomposite from 35% to 85% conversion, whereas the selectivity was 99%. A plausible mechanism was proposed. In fact, the cobalt porphyrin complex as a light sensitizer improves the photocatalytic activity through impregnation onto the TiO2 surface. The photocatalyst was reused several times without significant loss of its activity. Thus, this nanohybrid robust catalyst has excellent advantages such as facile synthesis, high activity and selectivity, and use of O2 and other environmentally friendly oxidants under mild conditions towards aldehyde production.
- Askari, Parvin,Mohebbi, Sajjad
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p. 1715 - 1724
(2018/02/09)
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- Zirconium–Porphyrin-Based Metal–Organic Framework Hollow Nanotubes for Immobilization of Noble-Metal Single Atoms
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Single atoms immobilized on metal–organic frameworks (MOFs) with unique nanostructures have drawn tremendous attention in the application of catalysis but remain a great challenge. Various single noble-metal atoms have now been successfully anchored on the well-defined anchoring sites of the zirconium porphyrin MOF hollow nanotubes, which are probed by aberration-corrected scanning transmission electron microscopy and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy. Owing to the hollow structure and excellent photoelectrochemical performance, the HNTM-Ir/Pt exhibits outstanding catalytic activity in the visible-light photocatalytic H2 evolution via water splitting. The single atom immobilized on MOFs with hollow structures are expected to pave the way to expand the potential applications of MOFs.
- He, Ting,Chen, Shuangming,Ni, Bing,Gong, Yue,Wu, Zhao,Song, Li,Gu, Lin,Hu, Wenping,Wang, Xun
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supporting information
p. 3493 - 3498
(2018/02/27)
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- Carbene insertion into N-H bonds with size-selectivity induced by a microporous ruthenium-porphyrin metal-organic framework
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A stable and porous porphyrinic metal-organic framework, Ru-PMOF-1(Hf), has been prepared through the self-assembly of [5,10,15,20-tetrakis(4-carboxyphenyl)porphyrinato](monocarbonyl)ruthenium (Ru(TCPP)(CO)) and HfCl4. Single-crystal X-ray diff
- Chen, Lianfen,Cui, Hao,Wang, Yanhu,Liang, Xiang,Zhang, Li,Su, Cheng-Yong
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p. 3940 - 3946
(2018/03/21)
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- Direct evidence of charge separation in a metal-organic framework: Efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer
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The selective aerobic oxidative coupling of amines under mild conditions is an important laboratory and commercial procedure yet a great challenge. In this work, a porphyrinic metal-organic framework, PCN-222, was employed to catalyze the reaction. Upon visible light irradiation, the semiconductor-like behavior of PCN-222 initiates charge separation, evidently generating oxygen-centered active sites in Zr-oxo clusters indicated by enhanced porphyrin π-cation radical signals. The photogenerated electrons and holes further activate oxygen and amines, respectively, to give the corresponding redox products, both of which have been detected for the first time. The porphyrin motifs generate singlet oxygen based on energy transfer to further promote the reaction. As a result, PCN-222 exhibits excellent photocatalytic activity, selectivity and recyclability, far superior to its organic counterpart, for the reaction under ambient conditions via combined energy and charge transfer.
- Xu, Caiyun,Liu, Hang,Li, Dandan,Su, Ji-Hu,Jiang, Hai-Long
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p. 3152 - 3158
(2018/03/30)
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- Iron-based metalloporphyrins as efficient catalysts for aerobic oxidation of biomass derived furfural into maleic acid
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A series of porphyrin type catalysts with the metal active sites of Fe were prepared and investigated in aerobic oxidation of biomass-based furfural to maleic acid (MAD) in aqueous phase. The catalytic performance of meso-tetrakis(4-bromophenyl)porphyrin iron (III) chloride (FeT(p-Br)PPCl) immobilized on different supports was evaluated. It was interesting to find that the catalytic activity varied with the supports and followed the trend: FeT(p-Br)PPCl/SBA–15 > FeT(p-Br)PPCl/meso-ZSM–5 > FeT(p-Br)PPCl/MCM-41. The effect of reaction conditions were discussed in detail over FeT(p-Br)PPCl/SBA-15 catalyst, and 56.1% yield and 73.8% selectivity of MAD were obtained from renewable furfural under the optimal conditions. Moreover, the FeT(p-Br)PPCl/SBA-15 catalyst could be reused five times without a significant decrease of activity in recycling examinations.
- Xie, Yongdi,Huang, Yi,Wu, Chunyan,Yuan, Wenwen,Xia, Yongmei,Liu, Xiang,Wang, Haijun
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- Dual-Emitting Fluorescent Metal-Organic Framework Nanocomposites as a Broad-Range pH Sensor for Fluorescence Imaging
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pH plays an important role in understanding physiological/pathologic processes, and abnormal pH is a symbol of many common diseases such as cancer, stroke, and Alzheimer's disease. In this work, an effective dual-emission fluorescent metal-organic framework nanocomposite probe (denoted as RB-PCN) has been constructed for sensitive and broad-range detection of pH. RB-PCN was prepared by encapsulating the DBI-PEG-NH2-functionalized Fe3O4 into Zr-MOFs and then further reacting it with rhodamine B isothiocyanates (RBITC). In RB-PCN, RBITC is capable of sensing changes in pH in acidic solutions. Zr-MOFs not only enrich the target analyte but also exhibit a fluorescence response to pH changes in alkaline solutions. Based on the above structural and compositional features, RB-PCN could detect a wide range of pH changes. Importantly, such a nanoprobe could "see" the intracellular pH changes by fluorescence confocal imaging as well as "measure" the wider range of pH in actual samples by fluorescence spectroscopy. To the best of our knowledge, this is the first time a MOF-based dual-emitting fluorescent nanoprobe has been used for a wide range of pH detection.
- Chen, Haiyong,Wang, Jing,Shan, Duoliang,Chen, Jing,Zhang, Shouting,Lu, Xiaoquan
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p. 7056 - 7063
(2018/05/15)
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- From Metal–Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media
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It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed-ligand strategy to afford high-content (1.76 wt %) single-atom (SA) iron-implanted N-doped porous carbon (FeSA-N-C) via pyrolysis. Thanks to the single-atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized FeSA-N-C exhibits excellent oxygen reduction activity and stability, surpassing almost all non-noble-metal catalysts and state-of-the-art Pt/C, in both alkaline and more challenging acidic media. More far-reaching, this MOF-based mixed-ligand strategy opens a novel avenue to the precise fabrication of efficient single-atom catalysts.
- Jiao, Long,Wan, Gang,Zhang, Rui,Zhou, Hua,Yu, Shu-Hong,Jiang, Hai-Long
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p. 8525 - 8529
(2018/07/14)
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- A porous metal-organic aerogel based on dirhodium paddle-wheels as an efficient and stable heterogeneous catalyst towards the reduction reaction of aldehydes and ketones
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A new metal-organic aerogel (MOA-Rh-2) containing dirhodium paddle-wheels has been prepared from the reaction of dirhodium(ii) tetracarboxylate (Rh2(OAc)4) and tetrakis(4-carboxyphenyl)porphyrin (TCPP) in a mixed solvent of DMF and water, followed by supercritical CO2 extraction. MOA-Rh-2 has been fully characterized by ICP-OES, EDS, XPS, PXRD, SEM, TEM and TGA. Its porosity has been confirmed by N2 adsorption isotherms at 77 K, and the Barrett-Joyner-Halenda pore size is centered at 3.5 nm. The existence of mesopores has been further verified by dye adsorption tests using methylene blue (14.4 × 6.1 ?2) and rhodamine B (15.8 × 11.8 × 6.8 ?3). MOA-Rh-2 is air and moisture-stable. The catalytic results show that, under an air atmosphere and at ambient temperature, a low loading (0.1-0.4 mol%) of MOA-Rh-2 can efficiently promote the hydrosilylation of aldehydes and ketones with the commercially available silane of PhSiH3. After catalytic reactions, MOA-Rh-2 can be recycled and reused for 5 runs without significant loss of the activity, and the reaction conversions are in the range of 89-99%.
- Liu, Gang,Wang, Yanhu,Zhu, Baofu,Zhang, Li,Su, Cheng-Yong
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supporting information
p. 11358 - 11363
(2018/07/24)
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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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- Method for inhibiting photo-corrosion on cadmium sulfide
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The invention discloses a method for inhibiting photo-corrosion on cadmium sulfide. The method comprises the step of modifying the surface of cadmium sulfide by using zinc tetrahydrazide phenyl porphyrin, wherein the zinc tetrahydrazide phenyl porphyrin c
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Paragraph 0025; 0027; 0028
(2018/10/11)
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- Cis -Decalin oxidation as a stereochemical probe of in-MOF versus on-MOF catalysis
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Development of catalyst-controlled C-H hydroxylation could provide direct access to valuable synthetic targets, such as primary metabolites. Here, we report a new family of porous materials, comprised of 2-dimensional metalloporphyrin layers and flexible aliphatic linkers, and demonstrate C-H hydroxylation activity. We demonstrate that the stereochemistry of cis-decalin oxidation provides a useful tool for differentiating catalysis in from catalysis on porous materials, which is critical to leveraging the potential of porous materials for catalyst-controlled oxidation chemistry.
- Cardenal, Ashley D.,Jeong Park, Hye,Chalker, Cody J.,Ortiz, Kacey G.,Powers, David C.
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supporting information
p. 7377 - 7380
(2017/07/11)
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