Publications by authors named "Ali Morsali"

173 Publications

Instantaneous Sonophotocatalytic Degradation of Tetracycline over [email protected] Core-Shell Nanorods as a Robust and Eco-friendly Catalyst.

Inorg Chem 2021 Jul 23;60(13):9660-9672. Epub 2021 Jun 23.

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisbon 1049-001, Portugal.

The universal pollution of diverse water bodies and declined water quality represent very important environmental problems. The development of new and efficient photocatalytic water treatment systems based on the Z-scheme mechanisms can contribute to tackling such problems. This study reports the preparation, full characterization, and detailed sonophotocatalytic activity of a new series of hybrid [email protected] nanocomposites, which comprise a p-n heterojunction of 3D Zr(IV) metal-organic framework nanorods (NU-1000) and photoactive ZnInS (ZIS) nanostars. Among the obtained materials with varying content of ZIS (5, 10, 20, and 30%) on the surface of NU-1000, the [email protected] nanocomposite revealed an ultrahigh catalytic performance and recyclability in a quick visible-light-induced degradation of the tetracycline antibiotic in water under sonophotocatalytic conditions. Moreover, increased activity of [email protected] can be ascribed to the formation of a p-n heterojunction between NU-1000 and ZIS, and a synergistic effect of these components, leading to a high level of radical production, facilitating a Z-scheme charge carrier transfer and reducing the recombination of charge carriers. The radical trapping tests revealed that OH, O, and h are the major active species in the sonophotocatalytic degradation of tetracycline. Possible mechanism and mineralization pathways were introduced. Cytotoxicity of [email protected] and aquatic toxicity of water samples after tetracycline degradation were also assessed, showing good biocompatibility of the catalyst and efficacy of sonophotocatalytic protocols to produce water that does not affect the growth of bacteria. Finally, the obtained nanocomposites and developed photocatalytic processes can represent an interesting approach toward diverse environmental applications in water remediation and the elimination of other types of organic pollutants.
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http://dx.doi.org/10.1021/acs.inorgchem.1c00951DOI Listing
July 2021

Impact of Pore Size and Defects on the Selective Adsorption of Acetylene in Alkyne-Functionalized Nickel(II)-Pyrazolate-Based MOFs.

Chemistry 2021 Jun 11. Epub 2021 Jun 11.

Departamento de Química, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain.

C H /CO separation is a highly challenging process as a consequence of their similar physicochemical properties. In this work we have explored, by static and dynamic gas sorption techniques and computational modelling, the suitability of a series of two isoreticular robust Ni(II)pyrazolate-based MOFs, bearing alkyne moieties on the ligand backbones, for C H /CO separation. The results are consistent with high adsorption capacity and selectivity of the essayed systems towards C H molecules. Furthermore, a post-synthetic treatment with KOH ethanolic solution gives rise to linker vacancy defects and incorporation of extraframework potassium ions. Creation of defects is responsible for increased adsorption capacity for both gases, however, strong interactions of the cluster basic sites and extraframework potassium cations with CO molecules are responsible for a lowering of C H over CO selectivity.
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http://dx.doi.org/10.1002/chem.202100821DOI Listing
June 2021

Nanoscale Metal-Organic Frameworks: Recent developments in synthesis, modifications and bioimaging applications.

Chemosphere 2021 Oct 12;281:130717. Epub 2021 May 12.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran. Electronic address:

Porous Metal-Organic Frameworks (MOFs) have emerged as eye-catching materials in recent years. They are widely used in numerous fields of chemistry thanks to their desirable properties. MOFs have a key role in the development of bioimaging platforms that are hopefully expected to effectually pave the way for accurate and selective detection and diagnosis of abnormalities. Recently, many types of MOFs have been employed for detection of RNA, DNA, enzyme activity and small-biomolecules, as well as for magnetic resonance imaging (MRI) and computed tomography (CT), which are valuable methods for clinical analysis. The optimal performance of the MOF in the bio-imaging field depends on the core structure, synthesis method and modifications processes. In this review, we have attempted to present crucial parameters for designing and achieving an efficient MOF as bioimaging platforms, and provide a roadmap for researchers in this field. Moreover, the influence of modifications/fractionalizations on MOFs performance has been thoroughly discussed and challenging problems have been extensively addressed. Consideration is mainly focused on the principal concepts and applications that have been achieved to modify and synthesize advanced MOFs for future applications.
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http://dx.doi.org/10.1016/j.chemosphere.2021.130717DOI Listing
October 2021

Radiochromic Hydrogen-Bonded Organic Frameworks for X-ray Detection.

Chemistry 2021 Jul 11;27(42):10957-10965. Epub 2021 Jun 11.

State Key Laboratory of Structural Chemistry, Fujian Institute of Innovation, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, 350002, Fuzhou, Fujian, P. R. China.

Porous materials have been investigated as efficient photochromic platforms for detecting hazardous radiation, while the utilization of hydrogen bonded organic frameworks (HOFs) in this field has remained intact. Herein, two HOFs were synthesized through self-assembly of tetratopic viologen ligand and formic acid (PFC-25, PFC-26), as a new class of "all-organic" radiochromic smart material, opening a gate for HOFs in this field. PFC-26 is active upon both X-ray and UV irradiation, while PFC-25 is only active upon X-ray irradiation. The same building block yet different radiochromic behaviors of PFC-25 and PFC-26 allow us to gain a deep mechanistic understanding of the factors that control the detection specificity. Theoretical and experimental studies reveal that the degree of π-conjugation of viologen ligand is highly related to the threshold energy of triggering a charge transfer, therefore being a vital factor for the particularity of radiochromic materials. Thanks to its convenient processibility, nanoparticle size, and UV silence, PFC-25 can be further fabricated into a portable naked-eye sensor for X-ray detection, which shows obvious color change with the merits of high transmittance contrast, good sensitivity (reproducible dose threshold of 3.5 Gy), and excellent stability. The work exhibits the promising practical potentials of HOF materials in photochromic technology.
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http://dx.doi.org/10.1002/chem.202101061DOI Listing
July 2021

Cancer in Iran 2008 to 2025: Recent incidence trends and short-term predictions of the future burden.

Int J Cancer 2021 Aug 21;149(3):594-605. Epub 2021 Apr 21.

Golestan Research Center of Gastroenterology and Hepatology, Golestan University of Medical Sciences, Gorgan, Iran.

Policymakers require estimates of the future number of cancer patients in order to allocate finite resources to cancer prevention, treatment and palliative care. We examine recent cancer incidence trends in Iran and present predicted incidence rates and new cases for the entire country for the year 2025. We developed a method for approximating population-based incidence from the pathology-based data series available nationally for the years 2008 to 2013, and augmented this with data from the Iranian National Population-based Cancer Registry (INPCR) for the years 2014 to 2016. We fitted time-linear age-period models to the recent incidence trends to quantify the future cancer incidence burden to the year 2025, delineating the contribution of changes due to risk and those due to demographic change. The number of new cancer cases is predicted to increase in Iran from 112 000 recorded cases in 2016 to an estimated 160 000 in 2025, a 42.6% increase, of which 13.9% and 28.7% were attributed to changes in risk and population structure, respectively. In terms of specific cancers, the greatest increases in cases are predicted for thyroid (113.8%), prostate (66.7%), female breast (63.0%) and colorectal cancer (54.1%). Breast, colorectal and stomach cancers were the most common cancers in Iran in 2016 and are predicted to remain the leading cancers nationally in 2025. The increasing trends in incidence of most common cancers in Iran reinforce the need for the tailored design and implementation of effective national cancer control programs across the country.
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http://dx.doi.org/10.1002/ijc.33574DOI Listing
August 2021

High performance of ultrasonic-assisted synthesis of two spherical polymers for enantioselective catalysis.

Ultrason Sonochem 2021 May 20;73:105499. Epub 2021 Feb 20.

Department of Chemistry, Faculty of Sciences, TarbiatModares University, P.O. Box 14117-13116, Tehran, Islamic Republic of Iran. Electronic address:

Chiral polymers have aroused great attention in among chiral supramolecular materials based on their features. Herein, for the first time, the synthesis of chiral polymeric composites (CMNPs/1,4-Zbtb & 1,3-Zbtb) have been reported with entrapment through three strategies: ultrasonic irradiation, solvothermal, and mechanical stirring. According to the obtained results, it is found that ultrasound-assisted synthesis can be considered as an inexpensive and efficient method than the others, from the point ofviewof energy and time consuming. In this strategy, encapsulation of chiral magnetic nanoparticles (CMNPs) by using tetrazole-based polymers (Zbtbs) happens, in-situly. These chiral sphere-like inorganic-organic polymers can be considered as core and shell composites with catalytic activity due to their acidic (semi unsaturated Zn: open metal sites) and basic (abundant basic nitrogens) centers. In these structures, the unprecedented chirality induction can happen from the core to shell by non-covalent interaction, easily. They could catalyze symmetric oxidation and asymmetric henry condensation to give chiral β-nitroalkanol. Circular dichroism and chiral gas chromatography were used to characterize the produced enantiomers. These chiral polymeric materials can be considered as unique acid-base bifunctional catalysts with efficient properties such as high stability, enantiomeric excess, enantioselectivity to the main product, and protecting from CMNPs leaching.
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http://dx.doi.org/10.1016/j.ultsonch.2021.105499DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7937831PMC
May 2021

Stable supercapacitor electrode based on two-dimensional high nucleus silver nano-clusters as a green energy source.

Dalton Trans 2021 Feb 1;50(7):2606-2615. Epub 2021 Feb 1.

College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.

Atomically precise silver nanoclusters (Ag-NCs) are known as a hot research area owing to their brilliant features and they have attracted an immense amount of research attention over the last year. There is a lack of sufficient understanding about the Ag-NC synthesis mechanisms that result in optimal silver nanoclusters with an appropriate size, shape, and morphology. In addition, the coexisting flexible coordination of silver ions, the argentophilic interactions, and coordination bonds result in a high level of sophistication in the self-assembly process. Furthermore, the expansion of clusters by the organic ligand to form a high dimensional structure could be very interesting and useful for novel applications in particular. In this study, a novel two-dimensional 14-nucleus silver poly-cluster was designed and synthesized by the combination of two synthetic methods. The high nucleus silver cluster units are connected together via tetradecafluoroazelaic acid (CF) and this leads to the high stability of the polymer. This highly stable conductive poly-cluster, with bridging groups of difluoromethylene, displays a high energy density (372 F g at 4.5 A g), excellent cycling stability, and great capacity. This nanocluster shows a high power density and long cycle life over 6000 cycles (95%) and can also tolerate a wide range of scan rates (5 mV s to 1 V s), meaning it could act as a green energy source.
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http://dx.doi.org/10.1039/d0dt03608kDOI Listing
February 2021

New 3D Porous Silver Nanopolycluster as a Highly Effective Supercapacitor Electrode: Synthesis and Study of the Optical and Electrochemical Properties.

Inorg Chem 2021 Feb 20;60(3):1523-1532. Epub 2021 Jan 20.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14115-175, Iran.

A high-nucleus silver nanopolycluster as a new type of silver-based polymer supercapacitor (SSc) by a simple and single-step synthesis process was designed and synthesized. The structural, optical, and electrochemical properties of SSc-2 were determined. This highly stable conductive 3D nanopolycluster shows great cycling stability, large capacity, and high energy density without any modification or doping process and so acts as an excellent SSc (412 F g at 1.5 A g). In addition, there was a stable cycling performance (94% capacitance) following 7000 cycles at 3 A g current density. The presence of fluorinated groups, 3D expansion of high-nucleus metallic clusters, and porosity are the advantages of SSc-2 that lead to stability, conductivity, and high capacity, respectively. These results lead to the development of a novel kind of SSc by overcoming the low conductivity and limited capacity challenges without any modification.
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http://dx.doi.org/10.1021/acs.inorgchem.0c02875DOI Listing
February 2021

Simultaneous Presence of Open Metal Sites and Amine Groups on a 3D Dy(III)-Metal-Organic Framework Catalyst for Mild and Solvent-Free Conversion of CO to Cyclic Carbonates.

Inorg Chem 2021 Feb 15;60(3):2056-2067. Epub 2021 Jan 15.

School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, United Kingdom.

Carbon dioxide (CO) fixation to generate chemicals and fuels is of high current importance, especially toward finding mild and efficient strategies for catalytic CO transformation to value added products. Herein, we report a novel Lewis acid-base bifunctional amine-functionalized dysprosium(III) metal-organic framework [Dy(data)·2DMF]·DMF (2,5-data: 2,5-diamino-terephthalate), NH-TMU-73. This compound was fully characterized and its crystal structure reveals a 3D metal-organic framework (MOF) with micropores and free NH groups capable of promoting the chemical fixation of CO to cyclic carbonates. NH-TMU-73 is built from the Dy(III) centers and data blocks, which are arranged into an intricate underlying net with a rare type of topology. After activation, NH-TMU-73 and its terephthalate-based analogue (TMU-73) were applied for CO-to-epoxide coupling reactions to produce cyclic carbonates. Important features of this catalytic process concern high efficiency and activity in the absence of cocatalyst, use of solvent-free medium, atmospheric CO pressure, and ambient temperature conditions. Also, NH-TMU-73 features high structural stability and can be recycled and reused in subsequent catalytic tests. An important role of free amino groups and open metal sites in the MOF catalyst was highlighted when suggesting a possible reaction mechanism.
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http://dx.doi.org/10.1021/acs.inorgchem.0c03634DOI Listing
February 2021

Solvent-tuned ultrasonic synthesis of 2D coordination polymer nanostructures and flakes.

Ultrason Sonochem 2021 Apr 24;72:105425. Epub 2020 Dec 24.

Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus UAB, Bellaterra, 08193 Barcelona, Spain. Electronic address:

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu(L)(DMF)}, where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(HO)]·HO} (complex 2). On the other hand, ultrasound is required to induce the nanostructuration. Remarkably, different morphologies are obtained using different solvents and interconversion from one morphology to another seems to occur upon solvent exchange. Both complexes 1 and 2, as well as the corresponding nanostructures, have been fully characterized by different means such as infrared spectroscopy, x-ray diffraction and microscopy.
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http://dx.doi.org/10.1016/j.ultsonch.2020.105425DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7803821PMC
April 2021

Phenolic nitroaromatics detection by fluorinated metal-organic frameworks: Barrier elimination for selective sensing of specific group of nitroaromatics.

J Hazard Mater 2021 03 3;406:124501. Epub 2020 Dec 3.

College of Science & Engineering, James Cook University, Townsville, QLD 4811, Australia.

Many piesce of research have been performed to detect nitroaromatic-compounds (NACs) by metal-organic frameworks (MOFs). Despite extensive studies, there are still significant challenges like selective detection of specific NAC group in presence of other NACs. Here, we have integrated two functionalization strategies through decoration of pore-walls of the MOFs with trifluoromethyl groups and extension in π-conjugated system. Based on this idea, trifluoromethyl TMU-44 (with the formula [Zn(hfipbb)(L1)].DMF, Hhfipbb = 4,4'-(hexafluoroisopropylidene) bis(benzoic acid), L1 = N,N'-bis-pyridin-4-ylmethylene-benzene-1,4-diamine) and TMU-45 (with formula [Zn(hfipbb)(L2)].DMF, L2 = N,N'-bis-pyridin-4-ylmethylene-naphthalene-1,5-diamine) frameworks have been synthesized. The aromatic skeleton of TMU-44 is based on phenyl rings while TMU-45 aromatic skeleton is extended by replacement of phenyl with naphthyl core. Measurements reveal that these MOFs are highly sensitive to phenolic NACs especially 2,4,6-trinitrophenol (TNP) with high quenching efficiency of 90% for TMU-44 (K = 10,652 M, LOD = 6.9 ppm) and 99% for TMU-45 (K = 34,741 M, LOD = 2.07 ppm). The proposed detection mechanism can be associated with hydrogen bonding between OH group of phenolic NACs and trifluoromethyl groups of TMU-MOFs as well as π(rich)∙∙∙π(deficient) interaction between π-conjugated backbone of TMU-frameworks and π-deficient ring of NACs.
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http://dx.doi.org/10.1016/j.jhazmat.2020.124501DOI Listing
March 2021

Construction of an Asymmetric Porphyrinic Zirconium Metal-Organic Framework through Ionic Postchiral Modification.

Inorg Chem 2021 Jan 13;60(1):206-218. Epub 2020 Dec 13.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran.

Herein, one kind of neutral chiral zirconium metal-organic framework (Zr-MOF) was reported from the porphyrinic MOF (PMOF) family with a metallolinker (Mn-porphyrin) as the achiral polytopic linker [free base tetrakis(4-carboxyphenyl)porphyrin] and chiral anions. Achiral Zr-MOF was chiralized through the exchange of primitive anions with new chiral organic anions (postsynthetic exchange). This chiral functional porphyrinic MOF (CPMOF) was characterized by several techniques such as powder X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, H NMR, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller measurements. In the resulting structure, there are two active metal sites as Lewis acid centers (Zr and Mn) and chiral species as Brønsted acid sites along with their cooperation as nucleophiles. This CPMOF shows considerable bimodal porosity with high surface area and stability. Additionally, its ability was investigated in asymmetric catalyses of prochiral substrates. Interactions between framework chiral species and prochiral substrates have large impacts on the catalytic ability and chirality induction. This chiral catalyst proceeded asymmetric epoxidation and CO fixation reactions at lower pressure with high enantioselectivity due to Lewis acids and chiral auxiliary nucleophiles without significant loss of activity up to the sixth step of consecutive cycles of reusability. Observations revealed that chiralization of Zr-MOF could happen by a succinct strategy that can be a convenient method to design chiral MOFs.
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http://dx.doi.org/10.1021/acs.inorgchem.0c02811DOI Listing
January 2021

Synthesis of Polycarboxylate Rhodium(II) Metal-Organic Polyhedra (MOPs) and their use as Building Blocks for Highly Connected Metal-Organic Frameworks (MOFs).

Angew Chem Int Ed Engl 2021 Mar 29;60(11):5729-5733. Epub 2021 Jan 29.

Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC, The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193, Barcelona, Spain.

Use of preformed metal-organic polyhedra (MOPs) as supermolecular building blocks (SBBs) for the synthesis of metal-organic frameworks (MOFs) remains underexplored due to lack of robust functionalized MOPs. Herein we report the use of polycarboxylate cuboctahedral Rh -MOPs for constructing highly-connected MOFs. Cuboctahedral MOPs were functionalized with carboxylic acid groups on their 12 vertices or 24 edges through coordinative or covalent post-synthetic routes, respectively. We then used each isolated polycarboxylate Rh -MOP as 12-c cuboctahedral or 24-c rhombicuboctahedral SBBs that, upon linkage with metallic secondary building units (SBUs), afford bimetallic highly-connected MOFs. The assembly of a pre-synthesized 12-c SBB with a 4-c paddle-wheel SBU, and a 24-c SBB with a 3-c triangular Cu SBU gave rise to bimetallic MOFs having ftw (4,12)-c or rht (3,24)-c topologies, respectively.
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http://dx.doi.org/10.1002/anie.202013839DOI Listing
March 2021

Reuse of Predesigned Dual-Functional Metal Organic Frameworks (DF-MOFs) after Heavy Metal Removal.

J Hazard Mater 2021 02 30;403:123696. Epub 2020 Aug 30.

College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, PR China. Electronic address:

Designing porous and functionalized adsorbents and achieving high efficiency in heavy metals removal from wastewater is in the spotlight of environmental science. On the other hand, upon removal, adsorbents are still highly hazardous requiring that great care be taken in its packaging, transporting and storing. A fundamental route in the synthesis of functional extended structures is the ability to combine different chemical entities in a controlled way in order to achieve high performance. Herein, we report the systematic design of dual-functionalized metal organic framework (TMU-81) by incorporating sulfonyl and amide groups for the removal of Cd(II), Cu(II) and Cr(II) ions from simulated aqueous solutions. TMU-81 showed significant enhancement in heavy metals uptake suggesting that the strong host - guest interactions between cations and the donor sites play a major role in adsorption process. The maximum adsorption capacity for Cd was 526 mg/g which is among the highest values reported for similar MOFs and other porous materials. The good performance in uptake and selectivity of TMU-81 can be attributed to the network structure that shaping the void, create mono-dimensional channels, decorated by exposed oxygen atom sites selective for Cadmium ion. Environmental "compatibility" of a treated MOFs was studied in order to evaluate its possible recycling as a new template for different applications by using pyrolysis method. Engineering of the pore surface provides a potential for MOF with a hybrid interface to act as a versatile tool for the design of multifunctional nanoparticles to meet specific application requirements.
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http://dx.doi.org/10.1016/j.jhazmat.2020.123696DOI Listing
February 2021

Electrochemical Applications of Ferrocene-Based Coordination Polymers.

Chempluschem 2020 11;85(11):2397-2418

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box, 14155-4838, Tehran, Iran.

Ferrocene and its derivatives, especially ferrocene-based coordination polymers (Fc-CPs), offer the benefits of high thermal stability, two stable redox states, fast electron transfer, and excellent charge/discharge efficiency, thus holding great promise for electrochemical applications. Herein, we describe the synthesis and electrochemical applications of Fc-CPs and reveal how the incorporation of ferrocene units into coordination polymers containing other metals results in unprecedented properties. Moreover, we discuss the usage of Fc-CPs in supercapacitors, batteries, and sensors as well as further applications of these polymers, for example in electrocatalysts, water purification systems, adsorption/storage systems.
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http://dx.doi.org/10.1002/cplu.202000584DOI Listing
November 2020

Size-Selective Urea-Containing Metal-Organic Frameworks as Receptors for Anions.

Inorg Chem 2020 Nov 29;59(22):16421-16429. Epub 2020 Oct 29.

Dipartimento di Chimica, Università degli Studi di Milano, Milano 20133, Italy.

Anion recognition by neutral hosts that function in aqueous solution is an emerging area of interest in supramolecular chemistry. The design of neutral architectures for anion recognition still remains a challenge. Among neutral anion receptor systems, urea and its derivatives are considered as "privileged groups" in supramolecular anion recognition, since they have two proximate polarized N-H bonds exploitable for anion recognition. Despite promising advancements in urea-based structures, the strong hydrogen bond drives detrimental self-association. Therefore, immobilizing urea fragments onto the rigid structures of a metal-organic framework (MOF) would prevent this self-association and promote hydrogen-bond-accepting substrate recognition. With this aim, we have synthesized two new urea-containing metal-organic frameworks, namely [Zn(bpdc)(L2)]·DMF () and [Zn(bdc)(L2)]·2DMF () (bpdc = biphenyl-4,4'-dicarboxylate; bdc = terephthalate; L2 = 1,3-bis(pyridin-4-yl)urea), and we have assessed their recognition ability toward different anions in water. The two MOFs show good water stability and anion affinity, with a particular selectivity toward dihydrogen arsenate for and toward fluoride for . Crystal structure characterizations reveal 3-fold and 2-fold interpenetrated 3D networks for and , respectively, where all single interpenetrated networks are hydrogen bonded to each other in both cases. Despite the absence of self-quenching, the N-H urea bonds are tightly hydrogen bonded to the oxygen atoms of the dicarboxylate ligands and cannot be directly involved in the recognition process. The good performance in anion sensing and selectivity of the two MOFs can be ascribed to the network interpenetration that, shaping the void, creates monodimensional channels, decorated by exposed oxygen atom sites selective for arsenate sensing in and isolated cavities, covered by phenyl groups selective for fluoride recognition in .
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http://dx.doi.org/10.1021/acs.inorgchem.0c02215DOI Listing
November 2020

An applied quantum-chemical model for genipin-crosslinked chitosan (GCS) nanocarrier.

Int J Biol Macromol 2020 Dec 8;165(Pt A):1229-1240. Epub 2020 Oct 8.

Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran; Research Center for Animal Development Applied Biology, Mashhad Branch, Islamic Azad University, Mashhad 917568, Iran.

The genipin-crosslinked chitosan (GCS) nanocarrier has received a lot of attention due to its unique biological and chemical properties as an effective drug delivery system. GCS was modeled by considering two chitosan (CS) polymer sequences with six monomer units that are crosslinked by genipin. To investigate the characteristics of this model, we considered it as a nanocarrier of the anti-cancer drug cladribine (2CdA). Seven configurations of GCS and 2CdA (GCS/2CdA1-7) were optimized at M06-2X/6-31G(d,p) in aqueous solution. The average binding energy above 100 kJ mol indicates a high drug loading amount. The high adsorption of the drug on GCS is due to the hydrogen bonds that were investigated by AIM analysis. Hydrogen bonds also allow the drug to be released more slowly. These results were confirmed by experimental evidence and the comparison of this model with the simple model of one polymer chain. Also, the mechanism of GCS formation was investigated by calculating the activation parameters, which indicates that solvent (HO) molecules are explicitly involved in the formation of GCS.
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http://dx.doi.org/10.1016/j.ijbiomac.2020.10.013DOI Listing
December 2020

Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage.

Angew Chem Int Ed Engl 2021 May 3;60(20):11048-11067. Epub 2020 Dec 3.

Beijing Key Lab of Theory and Technology for Advanced Battery Materials, Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, 100871, China.

Supercapacitors (SCs), showing excellent power density, long service life, and high reversibility, have received great attention because of the increasing demand for energy storage devices. To further improve their performance, it is essential to develop advanced electrode materials. One group of materials, porous crystalline solids referred to as metal-organic frameworks (MOFs), have proved to be excellent templates for synthesizing functional materials to be employed in the preparation of electrodes for SCs. In comparison to monometallic MOFs, bimetallic MOFs and their derivatives offer a number of advantages, including tunable electrochemical activity, high charge capacity, and improved electrical conductivity. This review focuses on the use of MOF-derived bimetallic materials in SCs, the origin of the improved performance, and the latest developments in the field. Furthermore, the challenges and perspectives in this research area are discussed.
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http://dx.doi.org/10.1002/anie.202010093DOI Listing
May 2021

Development of Porous Cobalt-/Copper-Doped Carbon Nanohybrids Derived from Functionalized MOFs as Efficient Catalysts for the Ullmann Cross-Coupling Reaction: Insights into the Active Centers.

ACS Appl Mater Interfaces 2020 Sep 9;12(38):43115-43124. Epub 2020 Sep 9.

Service de Cristallochimie, Université Paris-Saclay, Institut de Chimie des Substances Naturelles-CNRS, Bât 27, 1 Avenue de la Terrasse, Gif sur Yvette 91190, France.

Newly emerging poly-functional metal-organic frameworks (MOFs) have been proved to be a promising alternative method for the hard/soft template to generate different carbon-based heterostructures. Herein, we have synthesized a sulfonyl-amide-based MOF (TMU-81) with an exceptionally high concentration of functional groups, which can interact strongly with metal ions and utilized it as a double-template platform to fabricate versatile catalysts by remaining structural regularity. The preloaded copper ions resided in pores of TMU-81 not only play a significant role in pore-forming by in situ renovating into Cu nanoparticles via the pyrolysis process but also trigger the morphological transformations of the resultant metal/carbon hybrids. The morphology of the TMU-81 was tuned from truncated octahedron to cubic in cobalt-/copper-doped carbon nanohybrids (MC-81), and also the Brunauer-Emmett-Teller surface area increased significantly up to 1450 cm/g. Benchmarks have been established for the performance of TMU-81, pyrolyzed TMU-81 (P-TMU-81), and MC-81s, as efficient and robust catalysts for the C-N cross-coupling reaction with aryl-halides and amines. The obtained MC-81 showed superior performance compared with pristine TMU-81 and pyrolyzed P-TMU-81. The catalysis performance is found to be closely dependent on the amount of preloaded Cu ions in the MOFs. After 5 cycles, the catalysts were reusable without any significant loss of activity. Benefiting from the structural and compositional advantages, the present approach offers an intelligent way to synthesis and design of structurally complex MOF hybrid and derived functionalized systems.
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http://dx.doi.org/10.1021/acsami.0c09912DOI Listing
September 2020

Function-Topology Relationship in the Catalytic Hydrolysis of a Chemical Warfare Simulant in Two Zr-MOFs.

Chemistry 2020 Dec 24;26(72):17437-17444. Epub 2020 Nov 24.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, 14115175, Tehran, Iran.

Owing to their high surface area, high concentration of active metal sites, and water stability, zirconium(VI)-based metal-organic frameworks (Zr-MOFs) have shown excellent activity in the hydrolysis of organophosphorus nerve agents (OPNs). In this regard, for the first time, two topologically different Zr-MOFs (Zr-fcu-tmuc and Zr-bcu-tmuc, constructed from the same organic and inorganic building blocks; fcu=face-centered cubic, bcu=body-centered cubic) have been rationally chosen to investigate the effect of network topology on the catalytic hydrolysis of the nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP). A remarkable enhancement in the hydrolysis rate of DMNP was observed with Zr-bcu-tmuc, reducing the half-life more than three-fold compared with Zr-fcu-tmuc. Greater accessibility of the active Zr sites in the 8-connected bcu net compared with the 12-connected fcu leads to a faster hydrolysis of DMNP on Zr-bcu-tmuc. Interestingly, the higher activity of Zr-bcu-tmuc was also confirmed by its higher fluorescence sensitivity towards DMNP (limit of detection (LOD)=0.557 μm) compared with Zr-fcu-tmuc (LOD=1.09 μm). The results show that controlling the desired topology of Zr-MOFs is a useful strategy for improving their performance in the detection and catalytic detoxification of OPNs.
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http://dx.doi.org/10.1002/chem.202002412DOI Listing
December 2020

Ultrasonic-assisted synthesis of nano-sized metal-organic framework; a simple method to explore selective and fast Congo Red adsorption.

Ultrason Sonochem 2020 Dec 2;69:105246. Epub 2020 Jul 2.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14117-13116, Tehran, Islamic Republic of Iran. Electronic address:

A novel mixed linker Metal-organic Framework, [Co(NHIsoBDC)(bpfn)].DMF (TMU-69), with amide and amino functionalized spacers (bpfn = N,N'-(naphthalene-1,5-diyl)diisonicotinamide, NHIsoBDCH = 5-Aminoisophthalic acid) was synthesized through both solvothermal and ultrasonic approaches. Applying sonochemical irradiation led to ultrafast formation of Flower-shaped nanoplates of TMU-69 within 15 min with high yield while, solvothermal method takes 3 days to form the framework. Control of size and morphology was also enhanced through applying ultrasonic irradiations. The implication of applied time and concentration of reagents on size and morphology of nano-structured TMU-69 have been optimized. Applying higher concentration of initial material with optimized 60-minute irradiation forms uniform smaller sized nanoplates of TMU-69. Also, the efficiency of TMU-69 bulk and nanoplates toward removal of pollutant dyes from water was investigated. The selective adsorption of Congo Red was observed among other dyes. Also, drastic enhancement in removal kinetic of Congo Red through using ultrasonic assisted nanoplates of TMU-69 was obtained.
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http://dx.doi.org/10.1016/j.ultsonch.2020.105246DOI Listing
December 2020

Enhanced electrochemical oxygen and hydrogen evolution reactions using an [email protected] composite electrode in alkaline electrolyte.

Chem Commun (Camb) 2020 Jun;56(49):6652-6655

Department of Chemistry, Faculty of Basic Sciences, Tarbiat Modares University, Tehran, 14115-175, Iran.

A well-designed [email protected] ([email protected]) composite can offer efficient electrocatalytic performance with ultralow HER and OER overpotentials of 93 and 129 mV, respectively, at a current density of 10 mA cm-2 in 2 M KOH. Outstanding OER and HER activities of the composite could be attributed to the porosity and higher surface area of NU-1000 (NU), the layered structure of NiMn-LDHS (LDHS), abundant active sites in LDH, and synergistic interaction between NU and LDHS.
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http://dx.doi.org/10.1039/d0cc01146kDOI Listing
June 2020

Comparative Study of the Supercapacitive Performance of Three Ferrocene-Based Structures: Targeted Design of a Conductive Ferrocene-Functionalized Coordination Polymer as a Supercapacitor Electrode.

Chemistry 2020 Aug 20;26(43):9518-9526. Epub 2020 Jul 20.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, +98, Iran.

As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH) ) clusters based on coinage metals, [(PPh ) AgO CFcCO Ag(PPh ) ] ⋅7 CH OH (SC : super capacitor) and [(PPh ) CuO CFcCO Cu(PPh ) ]⋅3 CH OH (SC ), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g and 210 F g specific capacitance at 1.5 A g in Na SO electrolyte, respectively. The obtained results show that the presence of Cu instead of Ag improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC ([(PPh ) CuO CFcCO ] ), a polymeric structure of SC , was synthesized and used as an energy storage electrode. PSC displays high conductivity and gives 455 F g capacitance at 3 A g . The PSC as a supercapacitor electrode presents a high power density (2416 W kg ), high energy density (161 Wh kg ), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.
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http://dx.doi.org/10.1002/chem.202001109DOI Listing
August 2020

Net-Clipping: An Approach to Deduce the Topology of Metal-Organic Frameworks Built with Zigzag Ligands.

J Am Chem Soc 2020 May 6;142(20):9135-9140. Epub 2020 May 6.

Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain.

Herein we propose a new approach for deducing the topology of metal-organic frameworks (MOFs) assembled from organic ligands of low symmetry, which we call . It is based on the construction of nets by rational deconstruction of edge-transitive nets comprising higher-connected molecular building blocks (MBBs). We have applied net-clipping to predict the topologies of MOFs containing zigzag ligands. To this end, we derived 2-connected (2-c) zigzag ligands from 4-c square-like MBBs by first splitting the 4-c nodes into two 3-c nodes and then clipping their two diagonally connecting groups. We demonstrate that, when this approach is applied to the 17 edge-transitive nets containing square-like 4-c MBBs, net-clipping leads to generation of 10 nets with different underlying topologies. Moreover, we report that literature and experimental research corroborate successful implementation of our approach. As proof-of-concept, we employed net-clipping to form three new MOFs built with zigzag ligands, each of which exhibits the deduced topology.
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http://dx.doi.org/10.1021/jacs.0c03404DOI Listing
May 2020

Hexavalent Octahedral Template: A Neutral High-Nucleus Silver Alkynyl Nanocluster Emitting Infrared Light.

Inorg Chem 2020 May 13;59(10):6684-6688. Epub 2020 Apr 13.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14115-175, Iran.

The first silver nanocluster with an octahedral template of TeO was synthesized as a neutral 36-nucleus nanocluster, and its structure was demonstrated using single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, electrospray ionization mass spectrometry, and X-ray photoelectron spectroscopy. The peripheral ligands of the cagelike skeleton of the nanocluster are CFCOO and BuC≡C. During the synthesis, the TeO template arranged the nanocluster, and a 36-nucleus nanocluster was formed. The effect of the template nature was displayed on the structural features of the nanocluster in comparison with an 8-nucleus cluster, with the same synthesis conditions. The photoluminescence and UV-vis absorption analyses of the nanocluster were also investigated. The nanocluster displayed near-infrared luminescence emission at 690 nm.
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http://dx.doi.org/10.1021/acs.inorgchem.0c00665DOI Listing
May 2020

Rational morphology control of nano-scale amide decorated metal-organic frameworks by ultrasonic method: Capability to selective and sensitive detection of nitro explosives.

Ultrason Sonochem 2020 Sep 26;66:105110. Epub 2020 Mar 26.

Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Saclay, 1 Avenue de la Terrasse, 91190 Gif-sur-Yvette, France.

One of the key challenges in rational design and synthesis of metal-organic frameworks (MOFs) is defined control over size and morphology for using these materials in many more advanced applications. Combining ultrasonic method and capping groups makes it possible to control the size and change the morphology of metal organic frameworks without changing material compositions. Nano TMU-46, 47 and 48 with copper metal center and amide functionalized pillar were synthesized by using ultrasonic irritation and characterized by FE-SEM, powder X-ray diffraction, elemental analysis, and FTIR spectroscopy. Sensing properties of these nano scale materials and the correlation between the nano structure and nitroaromatic compounds detection were studied. Nano TMU-46 due to its special and porous structure and available functional group show strong luminescence emission, which is selectively sensitive to Trinitrophenol (TNP) with a detection limit of 10 M. Furthermore, multiple morphological transition in the structure of these crystals were observed with using different modulators. This morphology transition, in fact, successfully led to significant change in sensing properties of this structure and decreased the detection limit to 10 M.
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http://dx.doi.org/10.1016/j.ultsonch.2020.105110DOI Listing
September 2020

Coordinatively unsaturated metal sites (open metal sites) in metal-organic frameworks: design and applications.

Chem Soc Rev 2020 May 1;49(9):2751-2798. Epub 2020 Apr 1.

Institut für Anorganische Chemie und Strukturchemie, Heinrich-Heine-Universität Düsseldorf, D-40204 Düsseldorf, Germany.

Metal-organic frameworks (MOFs) can contain open metal sites (OMS) or coordinatively unsaturated sites (CUS) or open coordination sites (OCS) when vacant Lewis acid sites on the metal ions or cluster nodes have been generated. This review combines for the first time all aspects of OMS in MOFs, starting from different preparation strategies over theoretical studies on the effects of OMS with host-guest interactions up to distinct OMS-MOF applications. In the experimental part the focus of this review is on MOFs with proven OMS formation which are not only invoked but are clearly verified by analytical methods.
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http://dx.doi.org/10.1039/c9cs00609eDOI Listing
May 2020

Synthesis, Characterization and DNA Binding Investigations of a New Binuclear Ag(I) Complex and Evaluation of Its Anticancer Property.

Int J Nanomedicine 2020 12;15:953-964. Epub 2020 Feb 12.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran, Iran.

Aim: A new Ag(I) complex (A) was synthesized and evaluated for its anticancer activity against human cancer cell lines.

Materials And Methods: The complex A was characterized by H, C, and P nuclear magnetic resonance (NMR), infrared (IR) spectra, elemental analysis, and X-ray crystallography. The interaction of the complex with CT-DNA was studied by electronic absorption spectra, fluorescence spectroscopy, and cyclic voltammetry; cell viability (%) was assessed by absorbance measurement of the samples.

Results: The interaction mode of the complex A with DNA is electrostatic, and this complex shows good potential in anticancer properties against HCT 116 (human colorectal cancer cells) and MDA-MB-231 (MD Anderson-metastatic breast) cell lines with 0.5 micromolar concentrations.

Conclusion: The Ag(I) complex could interact with DNA noncovalently and has anticancer properties.
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http://dx.doi.org/10.2147/IJN.S225038DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7024786PMC
June 2020

Size and function influence study on enhanced catalytic performance of a cooperative MOF for mild, green and fast C-C bond formation.

Dalton Trans 2020 Mar;49(10):3234-3242

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155-4838, Tehran, Iran.

Tuning of pore function and size (surface area) are two key factors that play important roles in the performance of metal-organic-frameworks (MOFs) as catalysts. The catalytic performance of two bulk and nanosized MOFs with different functional groups such as a Brønsted base and Lewis acid was studied in line with the sustainable development of catalysts and green chemistry principles. Bifunctional imine decorated TMU-33, ([Cd3(BDC)3(OPP)(DMF)2]·2DMA)n (TMU-33), (OPP: N,N'-(oxybis(4,1-phenylene))bis(1-(pyridin-4yl)methanimine)), with an adjustable structure and amine functionalized TMU-40, [Zn(BDC)(L*)]·DMF, (L*: N1,N2-bis(pyridin-4-ylmethylene)ethane-1,2-diamine), were evaluated in the C-C bond forming reaction under mild and green conditions. The results show that the nanosized samples of bifunctional TMU-33 which simultaneously have an imine and open metal site exhibit higher performance as Knoevenagel catalysts. Furthermore, among the nanosized samples, the nanoplate TMU-33 with more access to open metal sites shows the highest catalytic activity without any side product in water, at room temperature for 5 min, which confirms that the Lewis acid is the effective catalyst for this reaction. The catalyst could be reused for at least three cycles without any significant loss of its activity. The performance of the structure indicates that the tuning of functionality of MOFs can be a very promising route for the extension of green catalysts.
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http://dx.doi.org/10.1039/d0dt00433bDOI Listing
March 2020

Dimension Control in Mixed Linker Metal-Organic Frameworks via Adjusting the Linker Shapes.

Inorg Chem 2020 Mar 14;59(5):2988-2996. Epub 2020 Feb 14.

Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14115-4838, Islamic Republic of Iran.

In this context, we describe a novel method to control the dimensionality and, further, the morphology in three mixed linker metal-organic frameworks (MOFs) TMU-70, TMU-71, and TMU-49 via altering the linker shapes. The compatibility between the shape of linkers used in the mixed linker framework, specifically linker angles, can directly affect the dimensionality of the resulting networks from 2D to 3D. Using incompatible linkers (one bent and one linear) together with binodal SBU directed the structure to form 2D networks, while 3D networks were obtained through applying linkers with the same shape. Further, the 2D and 3D MOFs were fabricated through the coordination modulation strategy. The impact of various modulators on the size and morphology of the structures has been examined. The 2D MOFs produced only nanorods through application of different capping agents owing to their preferred crystal growth, while the 3D networks led to rod and plate morphologies. Also, the catalytic performance of MOFs in an aldol-type condensation reaction was estimated. High and fast catalytic activity is detected in nanoscale rod-shaped catalysts.
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http://dx.doi.org/10.1021/acs.inorgchem.9b03293DOI Listing
March 2020
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