Mercury clathration-driven phase transition in a luminescent bipyrazolate metal-organic framework: a multitechnique investigation

Mercury is one of the most toxic heavy metals. By virtue of its triple bond, the novel ligand 1,2-bis(1H-pyrazol-4-yl)ethyne (H2BPE) was expressly designed and synthesized to devise metal-organic frameworks (MOFs) exhibiting high chemical affinity for mercury. Two MOFs, Zn(BPE) and Zn(BPE)·nDMF [interpenetrated i-Zn and noninterpenetrated ni-Zn·S, respectively; DMF = dimethylformamide], were isolated as microcrystalline powders. While i-Zn is stable in water for at least 15 days, its suspension in HgCl2 aqueous solutions prompts its conversion into HgCl2@ni-Zn. A multitechnique approach allowed us to shed light onto the observed HgCl2-triggered i-Zn-to-HgCl2@ni-Zn transformation at the molecular level. Density functional theory calculations on model systems suggested that HgCl2 interacts via the mercury atom with the carbon-carbon triple bond exclusively in ni-Zn. Powder X-ray diffraction enabled us to quantify the extent of the i-Zn-to-HgCl2@ni-Zn transition in 100-5000 ppm HgCl2 (aq) solutions, while X-ray fluorescence and inductively coupled plasma-mass spectrometry allowed us to demonstrate that HgCl2 is quantitatively sequestered from the aqueous phase. Irradiating at 365 nm, an intense fluorescence is observed at 470 nm for ni-Zn·S, which is partially quenched for i-Zn. This spectral benchmark was exploited to monitor in real time the i-Zn-to-HgCl2@ni-Zn conversion kinetics at different HgCl2 (aq) concentrations. A sizeable fluorescence increase was observed, within a 1 h time lapse, even at a concentration of 5 ppb. Overall, this comprehensive investigation unraveled an intriguing molecular mechanism, featuring the disaggregation of a water-stable MOF in the presence of HgCl2 and the self-assembly of a different crystalline phase around the pollutant, which is sequestered and simultaneously quantified by means of a luminescence change. Such a case study might open the way to new-conception strategies to achieve real-time sensing of mercury-containing pollutants in wastewaters and, eventually, pursue their straightforward and cost-effective purification

A familial form of epidermolysis bullosa simplex associated with a pathogenic variant in krt5

Epidermolysis bullosa simplex is a disease that belongs to a group of genodermatoses characterised by the formation of superficial bullous lesions caused by minor mechanical trauma to the skin. The skin fragility observed in the EBS is mainly caused by pathogenic variants in the KRT5 and KRT14 genes that compromise the mechanical stability of epithelial cells. By performing DNA sequencing in a female patient with EBS, we found the pathogenic variant c.967G>A (p.Val323Met) in the KRT5 gene. This variant co-segregated with EBS in the family pedigree and was transmitted in an autosomal dominant inheritance manner. This is the first report showing a familial form of EBS due to this pathogenic variant

Zirconium Metal-Organic Polyhedra with Dual Behavior for Organophosphate Poisoning Treatment

Organophosphate nerve agents and pesticides are extremely toxic compounds because they result in acetylcholinesterase (AChE) inhibition and concomitant nerve system damage. Herein, we report the synthesis, structural characterization, and proof-of-concept utility of zirconium metal-organic polyhedra (Zr-MOPs) for organophosphate poisoning treatment. The results show the formation of robust tetrahedral cages [((n-butylCpZr)3(OH)3O)4L6]Cl6(Zr-MOP-1; L = benzene-1,4-dicarboxylate, n-butylCp = n-butylcyclopentadienyl, Zr-MOP-10, and L = 4,4′-biphenyldicarboxylate) decorated with lipophilic alkyl residues and possessing accessible cavities of ∼9.8 and ∼10.7 Å inner diameters, respectively. These systems are able to both capture the organophosphate model compound diisopropylfluorophosphate (DIFP) and host and release the AChE reactivator drug pralidoxime (2-PAM). The resulting 2-PAM@Zr-MOP-1(0) host-guest assemblies feature a sustained delivery of 2-PAM under simulated biological conditions, with a concomitant reactivation of DIFP-inhibited AChE. Finally, 2-PAM@Zr-MOP systems have been incorporated into biocompatible phosphatidylcholine liposomes with the resulting assemblies being non-neurotoxic, as proven using neuroblastoma cell viability assays

Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags

The four zinc(II) mixed-ligand metal-organic frameworks (MIXMOFs) Zn(BPZ)x(BPZNO2)1-x, Zn(BPZ)x(BPZNH2)1-x, Zn(BPZNO2)x(BPZNH2)1-x, and Zn(BPZ)x(BPZNO2)y(BPZNH2)1-x-y (H2BPZ = 4,4′-bipyrazole; H2BPZNO2 = 3-nitro-4,4′-bipyrazole; H2BPZNH2 = 3-amino-4,4′-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO2, NH2), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from 13C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N2 adsorption at 77 K, they are micro-mesoporous materials with Brunauer-Emmett-Teller specific surface areas in the range 400-600 m2/g. A comparative study (involving also the single-ligand analogues) of CO2 adsorption capacity, CO2 isosteric heat of adsorption (Qst), and CO2/N2 selectivity in equimolar mixtures at p = 1 bar and T = 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Qst values and CO2/N2 selectivity vs the nitro-functionalized analogues; in addition, tag "dilution" [upon passing from Zn(BPZX) to Zn(BPZ)x(BPZX)1-x] increases CO2 adsorption selectivity over N2. The simultaneous presence of amino and nitro groups is not beneficial for CO2 uptake. Among the compounds studied, the best compromise among uptake capacity, Qst, and CO2/N2 selectivity is represented by Zn(BPZ)x(BPZNH2)1-x

UGIJAR AND CANJAYAR NEOGENE BASINS (SE SPAIN): AN EXAMPLE OF STRIKE-SLIP BASIN EVOLUTION IN TRANSPRESSIVE REGIME

The present study has been carried out in the eastern part of the Alpujarran corridor (Betic Chain), an E-W trending basin, 80 km long, of Neogene-Quaternary age. In particular, the Ugijar and Canjayar basins (respectively named Basin 1 and Basin 2), controlled by an E-W trending left stepping right lateral strike­slip system, associated with NE-SW trending thrust faults, have been investigated. The stratigraphic sequence of the forementioned two basins, which can be up to 2000 m thick, is mainly due to tectonic subsidence and is here interpreted in terms of Sequence Stratigraphy. The age of the whole sequence, dated by means of planktonic foraminifera, is Late Serravallian-Pliocene

Zirconium Metal−Organic Polyhedra with Dual Behavior for Organophosphate Poisoning Treatment

Organophosphate nerve agents and pesticides are extremely toxic compounds because they result in acetylcholinesterase (AChE) inhibition and concomitant nerve system damage. Herein, we report the synthesis, structural characterization, and proof-of-concept utility of zirconium metal−organic polyhedra (Zr-MOPs) for organophosphate poisoning treatment. The results show the formation of robust tetrahedral cages [((n-butylCpZr)3(OH)3O)4L6]Cl6 (Zr-MOP-1; L = benzene-1,4- dicarboxylate, n-butylCp = n-butylcyclopentadienyl, Zr-MOP-10, and L = 4,4′-biphenyldicarboxylate) decorated with lipophilic alkyl residues and possessing accessible cavities of ∼9.8 and ∼10.7 Å inner diameters, respectively. These systems are able to both capture the organophosphate model compound diisopropylfluorophosphate (DIFP) and host and release the AChE reactivator drug pralidoxime (2-PAM). The resulting 2-PAM@ Zr-MOP-1(0) host−guest assemblies feature a sustained delivery of 2-PAM under simulated biological conditions, with a concomitant reactivation of DIFP-inhibited AChE. Finally, 2-PAM@Zr-MOP systems have been incorporated into biocompatible phosphatidylcholine liposomes with the resulting assemblies being non-neurotoxic, as proven using neuroblastoma cell viability assays.Spanish MCIN/AEI PID2020-113608RB-I00FEDER/Junta de Andalucia-Conserjeria de Economia y Conocimiento B-FQM-364-UGR18 B-FQM-006-UGR18FEDER/Junta de Andalucia-Consejeria de Transformacion Economica, Industria, Conocimiento y Universidades P18-RT-612 P20_00672Fondazione CRUIprograma Juan de la Cierva FormacionSpanish Government PID2020-118117RB-I00Center for Forestry Research & Experimentation (CIEF)European Commission SEJIGENT/2021/059 PROMETEU/2021/054La Caixa Foundation 100010434 LCF/BQ/PR20/11770014"Maria de Maeztu" Program for Centers of Excellence in RD CEX2019-000919-MH2020-MSCA-IF2019-888972-PSust-MO

Arthroscopic treatment of an unusual distal clavicle ostheochondroma causing rotator cuff impingement: Case report and literature review

Chronic shoulder impingement is one of the most common causes of shoulder pain. Intrinsic, extrinsic and secondary factors play a role in this syndrome; however the etiology of the pathology is still under debate. In rare cases, it can be caused by tumors, such as an osteochondroma. In the present study, a 49-year-old patient presented with shoulder pain for 6 months. Initially he underwent conservative treatment, without relief of symptoms. X-rays and MRI were then performed and showed the presence of an exostotic formation on the undersurface of the lateral third of the clavicle. The formation was arthroscopically removed. Histologic examination confirmed the diagnosis of osteochondroma. After surgery, the patient resumed fully activities with no symptoms within 3 months. At 1 year follow up, there are still no clinical or radiological signs of recurrence. This is, to our knowledge, the first case where an arthroscopic approach was used to remove an ostochondroma of the distal third of the clavicle

Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00481"[EN] Three metal-organic frameworks with the general formula Co(BPZX) (BPZX(2-) = 3-X-4,4'-bipyrazolate, X = H, NH2, NO2) constructed with ligands having different functional groups on the same skeleton have been employed as heterogeneous catalysts for aerobic liquid-phase oxidation of cumene with O-2 as oxidant. O-2 adsorption isotherms collected at p(O2) = 1 atm and T = 195 and 273 K have cast light on the relative affinity of these catalysts for dioxygen. The highest gas uptake at 195 K is found for Co(BPZ) (3.2 mmol/g (10.1 wt % O-2)), in line with its highest BET specific surface area (926 m(2)/g) in comparison with those of Co(BPZNH(2)) (317 m(2)/g) and Co(BPZNO(2)) (645 m(2)/g). The O-2 isosteric heat of adsorption (Q(2)) trend follows the order Co(BPZ) > Co(BPZNH(2)) > Co(BPZNO(2)). Interestingly, the selectivity in the cumene oxidation products was found to be dependent on the tag present in the catalyst linker: while cumene hydroperoxide (CHP) is the main product obtained with Co(BPZ) (84% selectivity to CHP after 7 h, p(O2) = 4 bar, and T = 363 K), further oxidation to 2-phenyl-2-propanol (PP) is observed in the presence of Co(BPZNH(2)) as the catalyst (69% selectivity to PP under the same experimental conditions).S.G., R.V., and M.M. acknowledge Universita dell'Insubria for partial funding. G.G. thanks the Italian MIUR through the PRIN 2017 Project Multi-e: Multielectron Transfer for the Conversion of Small Molecules: an Enabling Technology for the Chemical Use of Renewable Energy (20179337R7) for financial support. G.G. thanks the TRAINER project (Catalysts for Transition to Renewable Energy Future) ref. ANR-17-MPGA-0017 for support. C.P. thanks the University of Camerino and the Italian MIUR throughout the PRIN 2015 Project Towards a Sustainable Chemistry (20154 x 9ATP_002). This project has also received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 641887 (project acronym: DEFNET) and the Spanish Government through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). Professor Norberto Masciocchi (University of Insubria, Como, Italy) is acknowledged for fruitful discussions. The authors are also grateful to Dr. Giulia Tuci (CNR-ICCOM Florence, Italy) for help with the XPS curve fitting. The Microscopy Service of the Universitat Politècnica de València is gratefully acknowledged for the electron microscopy measurements.Nowacka, AE.; Vismara, R.; Mercuri, G.; Moroni, M.; Palomino Roca, M.; Domasevitch, K.; Di Nicola, C.... (2020). Cobalt(II) Bipyrazolate Metal-Organic Frameworks as Heterogeneous Catalysts in Cumene Aerobic Oxidation: A Tag-Dependent Selectivity. Inorganic Chemistry. 59(12):8161-8172. https://doi.org/10.1021/acs.inorgchem.0c00481S816181725912Fortuin, J. P., & Waterman, H. I. (1953). Production of phenol from cumene. Chemical Engineering Science, 2(4), 182-192. doi:10.1016/0009-2509(53)80040-0Luyben, W. L. (2009). Design and Control of the Cumene Process. Industrial & Engineering Chemistry Research, 49(2), 719-734. doi:10.1021/ie9011535Matsui, S., & Fujita, T. (2001). New cumene-oxidation systems. Catalysis Today, 71(1-2), 145-152. doi:10.1016/s0920-5861(01)00450-3Opeida, I. A., Kytsya, A. R., Bazylyak, L. I., & Pobigun, O. I. (2017). Silver Nanoparticle Catalysis of the Liquid-Phase Radical Chain Oxidation of Cumene by Molecular Oxygen. Theoretical and Experimental Chemistry, 52(6), 369-374. doi:10.1007/s11237-017-9492-zTsodikov, M. V., Kugel, V. Y., Slivinskii, E. V., Bondarenko, G. N., Maksimov, Y. V., Alvarez, M. A., … Navio, J. A. (2000). Selectivity and mechanism of cumene liquid-phase oxidation in the presence of powdered mixed iron–aluminum oxides prepared by alkoxy method. Applied Catalysis A: General, 193(1-2), 237-242. doi:10.1016/s0926-860x(99)00438-xZhang, M., Wang, L., Ji, H., Wu, B., & Zeng, X. (2007). Cumene Liquid Oxidation to Cumene Hydroperoxide over CuO Nanoparticle with Molecular Oxygen under Mild Condition. Journal of Natural Gas Chemistry, 16(4), 393-398. doi:10.1016/s1003-9953(08)60010-9Hsu, Y. F., & Cheng, C. P. (1998). Mechanistic investigation of the autooxidation of cumene catalyzed by transition metal salts supported on polymer. Journal of Molecular Catalysis A: Chemical, 136(1), 1-11. doi:10.1016/s1381-1169(98)00016-8Hsu, Y. F., & Cheng, C. P. (1997). Polymer supported catalyst for the effective autoxidation of cumene to cumene hydroperoxide. Journal of Molecular Catalysis A: Chemical, 120(1-3), 109-116. doi:10.1016/s1381-1169(96)00442-6Ying Fang, H., Mei Huei, Y., & Cheu Pyeng, C. (1996). Autooxidation of cumene catalyzed by transition metal compounds on polymeric supports. Journal of Molecular Catalysis A: Chemical, 105(3), 137-144. doi:10.1016/1381-1169(95)00205-7Narulkar, D. D., Srivastava, A. K., Butcher, R. J., Ansy, K. M., & Dhuri, S. N. (2017). Synthesis and characterization of N3Py2 ligand-based cobalt(II), nickel(II) and copper(II) catalysts for efficient conversion of hydrocarbons to alcohols. Inorganica Chimica Acta, 467, 405-414. doi:10.1016/j.ica.2017.08.027Wang, R.-M., Duan, Z.-F., He, Y.-F., & Lei, Z.-Q. (2006). Heterogeneous catalytic aerobic oxidation behavior of Co–Na heterodinuclear polymeric complex of Salen-crown ether. Journal of Molecular Catalysis A: Chemical, 260(1-2), 280-287. doi:10.1016/j.molcata.2006.07.049Rogovin, M., & Neumann, R. (1999). Silicate xerogels containing cobalt as heterogeneous catalysts for the side-chain oxidation of alkyl aromatic compounds with tert-butyl hydroperoxide. Journal of Molecular Catalysis A: Chemical, 138(2-3), 315-318. doi:10.1016/s1381-1169(98)00207-6Konopińska, A. (2017). <i>N</i>-Hydroxyphthalimide as a Catalyst of Cumene Oxidation with Hydroperoxide. Modern Chemistry, 5(2), 29. doi:10.11648/j.mc.20170502.12VARMA, G. (1973). Heterogeneous catalytic oxidation of cumene (isopropyl benzene) in liquid phase. Journal of Catalysis, 28(2), 236-244. doi:10.1016/0021-9517(73)90006-7Collom, S. L., Bloomfield, A. J., & Anastas, P. T. (2016). Advancing Sustainable Manufacturing through a Heterogeneous Cobalt Catalyst for Selective C–H Oxidation. Industrial & Engineering Chemistry Research, 55(12), 3308-3312. doi:10.1021/acs.iecr.5b03674Scognamiglio, J., Jones, L., Letizia, C. S., & Api, A. M. (2012). Fragrance material review on 2-phenyl-2-propanol. Food and Chemical Toxicology, 50, S130-S133. doi:10.1016/j.fct.2011.10.011Rossin, A., Tuci, G., Luconi, L., & Giambastiani, G. (2017). Metal–Organic Frameworks as Heterogeneous Catalysts in Hydrogen Production from Lightweight Inorganic Hydrides. ACS Catalysis, 7(8), 5035-5045. doi:10.1021/acscatal.7b01495Chughtai, A. H., Ahmad, N., Younus, H. A., Laypkov, A., & Verpoort, F. (2015). Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chemical Society Reviews, 44(19), 6804-6849. doi:10.1039/c4cs00395kLiu, J., Chen, L., Cui, H., Zhang, J., Zhang, L., & Su, C.-Y. (2014). Applications of metal–organic frameworks in heterogeneous supramolecular catalysis. Chem. Soc. Rev., 43(16), 6011-6061. doi:10.1039/c4cs00094cGascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kLuo, S., Zeng, Z., Zeng, G., Liu, Z., Xiao, R., Chen, M., … Jiang, D. (2019). Metal Organic Frameworks as Robust Host of Palladium Nanoparticles in Heterogeneous Catalysis: Synthesis, Application, and Prospect. ACS Applied Materials & Interfaces, 11(36), 32579-32598. doi:10.1021/acsami.9b11990Deng, X., Li, Z., & García, H. (2017). Visible Light Induced Organic Transformations Using Metal-Organic-Frameworks (MOFs). Chemistry - A European Journal, 23(47), 11189-11209. doi:10.1002/chem.201701460Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2016). Metal-Organic Frameworks as Catalysts for Oxidation Reactions. Chemistry - A European Journal, 22(24), 8012-8024. doi:10.1002/chem.201505141Song, X., Hu, D., Yang, X., Zhang, H., Zhang, W., Li, J., … Yu, J. (2019). Polyoxomolybdic Cobalt Encapsulated within Zr-Based Metal–Organic Frameworks as Efficient Heterogeneous Catalysts for Olefins Epoxidation. ACS Sustainable Chemistry & Engineering, 7(3), 3624-3631. doi:10.1021/acssuschemeng.8b06736Zhang, T., Hu, Y.-Q., Han, T., Zhai, Y.-Q., & Zheng, Y.-Z. (2018). Redox-Active Cobalt(II/III) Metal–Organic Framework for Selective Oxidation of Cyclohexene. ACS Applied Materials & Interfaces, 10(18), 15786-15792. doi:10.1021/acsami.7b19323Ma, Y., Peng, H., Liu, J., Wang, Y., Hao, X., Feng, X., … Li, Y. (2018). Polyoxometalate-Based Metal–Organic Frameworks for Selective Oxidation of Aryl Alkenes to Aldehydes. Inorganic Chemistry, 57(7), 4109-4116. doi:10.1021/acs.inorgchem.8b00282Othong, J., Boonmak, J., Ha, J., Leelasubcharoen, S., & Youngme, S. (2017). Thermally Induced Single-Crystal-to-Single-Crystal Transformation and Heterogeneous Catalysts for Epoxidation Reaction of Co(II) Based Metal–Organic Frameworks Containing 1,4-Phenylenediacetic Acid. Crystal Growth & Design, 17(4), 1824-1835. doi:10.1021/acs.cgd.6b01788Wang, J.-C., Ding, F.-W., Ma, J.-P., Liu, Q.-K., Cheng, J.-Y., & Dong, Y.-B. (2015). Co(II)-MOF: A Highly Efficient Organic Oxidation Catalyst with Open Metal Sites. Inorganic Chemistry, 54(22), 10865-10872. doi:10.1021/acs.inorgchem.5b01938Tuci, G., Giambastiani, G., Kwon, S., Stair, P. C., Snurr, R. Q., & Rossin, A. (2014). Chiral Co(II) Metal–Organic Framework in the Heterogeneous Catalytic Oxidation of Alkenes under Aerobic and Anaerobic Conditions. ACS Catalysis, 4(3), 1032-1039. doi:10.1021/cs401003dHamidipour, L., & Farzaneh, F. (2013). Cobalt metal organic framework as an efficient heterogeneous catalyst for the oxidation of alkanes and alkenes. Reaction Kinetics, Mechanisms and Catalysis, 109(1), 67-75. doi:10.1007/s11144-012-0533-2Luz, I., León, A., Boronat, M., Llabrés i Xamena, F. X., & Corma, A. (2013). Selective aerobic oxidation of activated alkanes with MOFs and their use for epoxidation of olefins with oxygen in a tandem reaction. Catal. Sci. Technol., 3(2), 371-379. doi:10.1039/c2cy20449eSantiago-Portillo, A., Navalón, S., Cirujano, F. G., Xamena, F. X. L. i, Alvaro, M., & Garcia, H. (2015). MIL-101 as Reusable Solid Catalyst for Autoxidation of Benzylic Hydrocarbons in the Absence of Additional Oxidizing Reagents. ACS Catalysis, 5(6), 3216-3224. doi:10.1021/acscatal.5b00411Nowacka, A., Briantais, P., Prestipino, C., & Llabrés i Xamena, F. X. (2019). Selective Aerobic Oxidation of Cumene to Cumene Hydroperoxide over Mono- and Bimetallic Trimesate Metal–Organic Frameworks Prepared by a Facile «Green» Aqueous Synthesis. ACS Sustainable Chemistry & Engineering, 7(8), 7708-7715. doi:10.1021/acssuschemeng.8b06472Vismara, R., Tuci, G., Tombesi, A., Domasevitch, K. V., Di Nicola, C., Giambastiani, G., … Galli, S. (2019). Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags. ACS Applied Materials & Interfaces, 11(30), 26956-26969. doi:10.1021/acsami.9b08015Vismara, R., Tuci, G., Mosca, N., Domasevitch, K. V., Di Nicola, C., Pettinari, C., … Rossin, A. (2019). Amino-decorated bis(pyrazolate) metal–organic frameworks for carbon dioxide capture and green conversion into cyclic carbonates. Inorganic Chemistry Frontiers, 6(2), 533-545. doi:10.1039/c8qi00997jMosca, N., Vismara, R., Fernandes, J. A., Tuci, G., Di Nicola, C., Domasevitch, K. V., … Galli, S. (2018). Nitro-Functionalized Bis(pyrazolate) Metal-Organic Frameworks as Carbon Dioxide Capture Materials under Ambient Conditions. Chemistry - A European Journal, 24(50), 13170-13180. doi:10.1002/chem.201802240Pettinari, C., Tăbăcaru, A., & Galli, S. (2016). Coordination polymers and metal–organic frameworks based on poly(pyrazole)-containing ligands. Coordination Chemistry Reviews, 307, 1-31. doi:10.1016/j.ccr.2015.08.005Pettinari, C., Tăbăcaru, A., Boldog, I., Domasevitch, K. V., Galli, S., & Masciocchi, N. (2012). Novel Coordination Frameworks Incorporating the 4,4′-Bipyrazolyl Ditopic Ligand. Inorganic Chemistry, 51(9), 5235-5245. doi:10.1021/ic3001416Colombo, V., Montoro, C., Maspero, A., Palmisano, G., Masciocchi, N., Galli, S., … Navarro, J. A. R. (2012). Tuning the Adsorption Properties of Isoreticular Pyrazolate-Based Metal–Organic Frameworks through Ligand Modification. Journal of the American Chemical Society, 134(30), 12830-12843. doi:10.1021/ja305267mTăbăcaru, A., Pettinari, C., Masciocchi, N., Galli, S., Marchetti, F., & Angjellari, M. (2011). Pro-porous Coordination Polymers of the 1,4-Bis((3,5-dimethyl-1H-pyrazol-4-yl)-methyl)benzene Ligand with Late Transition Metals. Inorganic Chemistry, 50(22), 11506-11513. doi:10.1021/ic2013705Colombo, V., Galli, S., Choi, H. J., Han, G. D., Maspero, A., Palmisano, G., … Long, J. R. (2011). High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks with exposed metal sites. Chemical Science, 2(7), 1311. doi:10.1039/c1sc00136aMasciocchi, N., Galli, S., Colombo, V., Maspero, A., Palmisano, G., Seyyedi, B., … Bordiga, S. (2010). Cubic Octanuclear Ni(II) Clusters in Highly Porous Polypyrazolyl-Based Materials. Journal of the American Chemical Society, 132(23), 7902-7904. doi:10.1021/ja102862jGalli, S., Masciocchi, N., Colombo, V., Maspero, A., Palmisano, G., López-Garzón, F. J., … Navarro, J. A. R. (2010). Adsorption of Harmful Organic Vapors by Flexible Hydrophobic Bis-pyrazolate Based MOFs. Chemistry of Materials, 22(5), 1664-1672. doi:10.1021/cm902899tBoldog, I., Sieler, J., Chernega, A. N., & Domasevitch, K. V. (2002). 4,4′-Bipyrazolyl: new bitopic connector for construction of coordination networks. Inorganica Chimica Acta, 338, 69-77. doi:10.1016/s0020-1693(02)00902-7Domasevitch, K. V., Gospodinov, I., Krautscheid, H., Klapötke, T. M., & Stierstorfer, J. (2019). Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials. New Journal of Chemistry, 43(3), 1305-1312. doi:10.1039/c8nj05266bTOPAS-Academic 6; Bruker, by Coelho Software: Brisbane, Australia, 2016.Coelho, A. A. (2003). Indexing of powder diffraction patterns by iterative use of singular value decomposition. Journal of Applied Crystallography, 36(1), 86-95. doi:10.1107/s0021889802019878Cheetham, A. K., Bennett, T. D., Coudert, F.-X., & Goodwin, A. L. (2016). Defects and disorder in metal organic frameworks. Dalton Transactions, 45(10), 4113-4126. doi:10.1039/c5dt04392aCliffe, M. J., Wan, W., Zou, X., Chater, P. A., Kleppe, A. K., Tucker, M. G., … Goodwin, A. L. (2014). Correlated defect nanoregions in a metal–organic framework. Nature Communications, 5(1). doi:10.1038/ncomms5176Spirkl, S., Grzywa, M., & Volkmer, D. (2018). Synthesis and characterization of a flexible metal organic framework generated from MnIII and the 4,4′-bipyrazolate-ligand. Dalton Transactions, 47(26), 8779-8786. doi:10.1039/c8dt01185kNazarenko, O. M., Rusanov, E. B., Chernega, A. N., & Domasevitch, K. V. (2013). Cobalt(II) and cadmium(II) square grids supported with 4,4′-bipyrazole and accommodating 3-carboxyadamantane-1-carboxylate. Acta Crystallographica Section C Crystal Structure Communications, 69(3), 232-236. doi:10.1107/s0108270113003405Tăbăcaru, A., Pettinari, C., Marchetti, F., di Nicola, C., Domasevitch, K. V., Galli, S., … Cocchioni, M. (2012). Antibacterial Action of 4,4′-Bipyrazolyl-Based Silver(I) Coordination Polymers Embedded in PE Disks. Inorganic Chemistry, 51(18), 9775-9788. doi:10.1021/ic3011635Sun, Q.-F., Wong, K. M.-C., Liu, L.-X., Huang, H.-P., Yu, S.-Y., Yam, V. W.-W., … Yu, K.-C. (2008). Self-Assembly, Structures, and Photophysical Properties of 4,4′-Bipyrazolate-Linked Metallo-Macrocycles with Dimetal Clips. Inorganic Chemistry, 47(6), 2142-2154. doi:10.1021/ic701344pLozan, V., Solntsev, P. Y., Leibeling, G., Domasevitch, K. V., & Kersting, B. (2007). Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi2 Fragments Linked by 4,4′-Bipyrazolyl, 1,4-Bis(4′-pyrazolyl)benzene, and 4,4′-Bipyridazine: Synthesis, Structures, and Magnetic Properties. European Journal of Inorganic Chemistry, 2007(20), 3217-3226. doi:10.1002/ejic.200700317Bond distances and angles for the rigid body describing the ligand: C–C and C-N of the pyrazole ring 1.36 Å; exocyclic C–C 1.40 Å; C–H of the pyrazole ring 0.95 Å; C–NNH2 1.40 Å; N–H 0.95 Å; pyrazole ring internal and external bond angles 108 and 126°, respectively; angles at the nitrogen atom of the amino group 120°.Coelho, A. A. (2000). Whole-profile structure solution from powder diffraction data using simulated annealing. Journal of Applied Crystallography, 33(3), 899-908. doi:10.1107/s002188980000248xCheary, R. W., & Coelho, A. (1992). A fundamental parameters approach to X-ray line-profile fitting. Journal of Applied Crystallography, 25(2), 109-121. doi:10.1107/s0021889891010804Stephens, P. W. (1999). Phenomenological model of anisotropic peak broadening in powder diffraction. Journal of Applied Crystallography, 32(2), 281-289. doi:10.1107/s0021889898006001Rouquerol, J., Llewellyn, P., & Rouquerol, F. (2007). Is the bet equation applicable to microporous adsorbents? Characterization of Porous Solids VII - Proceedings of the 7th International Symposium on the Characterization of Porous Solids (COPS-VII), Aix-en-Provence, France, 26-28 May 2005, 49-56. doi:10.1016/s0167-2991(07)80008-5Saeidi, N., & Parvini, M. (2015). Accuracy of Dubinin-Astakov and Dubinin-Raduchkevic Adsorption Isotherm Models in Evaluating Micropore Volume of Bontonite. Periodica Polytechnica Chemical Engineering. doi:10.3311/ppch.8374Zhu, X., Tian, C., Veith, G. M., Abney, C. W., Dehaudt, J., & Dai, S. (2016). In Situ Doping Strategy for the Preparation of Conjugated Triazine Frameworks Displaying Efficient CO2 Capture Performance. Journal of the American Chemical Society, 138(36), 11497-11500. doi:10.1021/jacs.6b07644Zhu, X., Mahurin, S. M., An, S.-H., Do-Thanh, C.-L., Tian, C., Li, Y., … Dai, S. (2014). Efficient CO2 capture by a task-specific porous organic polymer bifunctionalized with carbazole and triazine groups. Chemical Communications, 50(59), 7933. doi:10.1039/c4cc01588fSpek, A. L. (2009). Structure validation in chemical crystallography. Acta Crystallographica Section D Biological Crystallography, 65(2), 148-155. doi:10.1107/s090744490804362xBlatov, V. A., Shevchenko, A. P., & Proserpio, D. M. (2014). Applied Topological Analysis of Crystal Structures with the Program Package ToposPro. Crystal Growth & Design, 14(7), 3576-3586. doi:10.1021/cg500498kTonigold, M., Lu, Y., Mavrandonakis, A., Puls, A., Staudt, R., Möllmer, J., … Volkmer, D. (2011). Pyrazolate-Based Cobalt(II)-Containing Metal-Organic Frameworks in Heterogeneous Catalytic Oxidation Reactions: Elucidating the Role of Entatic States for Biomimetic Oxidation Processes. Chemistry - A European Journal, 17(31), 8671-8695. doi:10.1002/chem.201003173Ma, S., & Zhou, H.-C. (2006). A Metal−Organic Framework with Entatic Metal Centers Exhibiting High Gas Adsorption Affinity. Journal of the American Chemical Society, 128(36), 11734-11735. doi:10.1021/ja063538zWang, Z.-J., Lv, J.-J., Yi, R.-N., Xiao, M., Feng, J.-J., Liang, Z.-W., … Xu, X. (2018). Nondirecting Group sp 3 C−H Activation for Synthesis of Bibenzyls via Homo-coupling as Catalyzed by Reduced Graphene Oxide Supported PtPd@Pt Porous Nanospheres. Advanced Synthesis & Catalysis, 360(5), 932-941. doi:10.1002/adsc.201701389CASEMIER, J. (1973). The oxidation of cumene and the decomposition of cumene hydroperoxide on silver, copper, and platinum. Journal of Catalysis, 29(3), 367-373. doi:10.1016/0021-9517(73)90242-xLiao, S., Chi, Y., Yu, H., Wang, H., & Peng, F. (2014). Tuning the Selectivity in the Aerobic Oxidation of Cumene Catalyzed by Nitrogen-Doped Carbon Nanotubes. ChemCatChem, 6(2), 555-560. doi:10.1002/cctc.201300909Silvestre-Albero, J. (2001). Characterization of microporous solids by immersion calorimetry. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 187-188(1-3), 151-165. doi:10.1016/s0927-7757(01)00620-3Everett, D. H. (1972). Manual of Symbols and Terminology for Physicochemical Quantities and Units, Appendix II: Definitions, Terminology and Symbols in Colloid and Surface Chemistry. Pure and Applied Chemistry, 31(4), 577-638. doi:10.1351/pac197231040577Liu, C., Wang, T., Ji, J., Wang, C., Wang, H., Jin, P., … Jiang, J. (2019). The effect of pore size and layer number of metal–porphyrin coordination nanosheets on sensing DNA. Journal of Materials Chemistry C, 7(33), 10240-10246. doi:10.1039/c9tc02778eGong, T., Yang, X., Fang, J.-J., Sui, Q., Xi, F.-G., & Gao, E.-Q. (2017). Distinct Chromic and Magnetic Properties of Metal–Organic Frameworks with a Redox Ligand. ACS Applied Materials & Interfaces, 9(6), 5503-5512. doi:10.1021/acsami.6b15540Yamada, Y., Kim, J., Matsuo, S., & Sato, S. (2014). Nitrogen-containing graphene analyzed by X-ray photoelectron spectroscopy. Carbon, 70, 59-74. doi:10.1016/j.carbon.2013.12.061Singhbabu, Y. N., Kumari, P., Parida, S., & Sahu, R. K. (2014). Conversion of pyrazoline to pyrazole in hydrazine treated N-substituted reduced graphene oxide films obtained by ion bombardment and their electrical properties. Carbon, 74, 32-43. doi:10.1016/j.carbon.2014.02.079Dementjev, A. ., de Graaf, A., van de Sanden, M. C. ., Maslakov, K. ., Naumkin, A. ., & Serov, A. . (2000). X-Ray photoelectr