Synthesis of bifunctional receptor for fluoride and cadmium based on calix[4]arene with thiourea moieties

Quiroga‐Campano, Cinthia; Gómez‐Machuca, Horacio; Moris, Silvana; Jara, Paul; Fuente, Julio R. De la; Pessoa‐Mahana, Hernán; Jullian, Carolina; Saitz, Claudio

doi:10.1016/j.molstruc.2017.03.089

Cited by 20 publications

(14 citation statements)

References 27 publications

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Section: Characterizationsupporting

confidence: 89%

“…The 1 H-NMR spectra of ligand L ( Figure 1) show two singlet signals for two sets of 18 t-Bu protons (δ 0.92 and 1.22 ppm), two doublet signals (δ 3.16, 4 protons, and 4.13 ppm 4 protons) assigned to the calixarene -CH 2 -bridging groups, a multiplet peak (δ 4.36-4.27 ppm) corresponding to the eight OCH 2 CH 2 NCS protons, two types of aromatic signals (δ 6.71, 4 protons, and 6.87 ppm, 4 protons) as two singlet signals assigned to the two types of calix [4]arene benzene ring protons, a multiplet peak (δ 6.83, 4 protons) and to two doublets of doublets (δ 6.99 ppm, 2 protons and 7.26 ppm, 2 protons) assigned to four types of aromatic protons of the phenol ring of the thiosemicarbazone arms, a singlet peak attributed to two OH protons of the calix [4]arene lower rim (δ 7.33 ppm), a singlet peak attributed to two thiosemicarbazone NH protons (δ 7.67 ppm), a singlet peak attributed to two NHCS protons (δ 8.68 ppm), a singlet peak attributed to two OH protons of the thiosemicarbazone phenol rings (δ 8.98 ppm), and a singlet peak related to two =CH imine protons (δ 9.74 ppm). The assignments of the 1 H-NMR spectrum are in agreement with literature data [48]. The 1 H-NMR spectra of ligand L ( Figure 1) show two singlet signals for two sets of 18 t-Bu protons (δ 0.92 and 1.22 ppm), two doublet signals (δ 3.16, 4 protons, and 4.13 ppm 4 protons) assigned to the calixarene -CH2-bridging groups, a multiplet peak (δ 4.36-4.27 ppm) corresponding to the eight OCH2CH2NCS protons, two types of aromatic signals (δ 6.71, 4 protons, and 6.87 ppm, 4 protons) as two singlet signals assigned to the two types of calix [4]arene benzene ring protons, a multiplet peak (δ 6.83, 4 protons) and to two doublets of doublets (δ 6.99 ppm, 2 protons and 7.26 ppm, 2 protons) assigned to four types of aromatic protons of the phenol ring of the thiosemicarbazone arms, a singlet peak attributed to two OH protons of the calix [4]arene lower rim (δ 7.33 ppm), a singlet peak attributed to two thiosemicarbazone NH protons (δ 7.67 ppm), a singlet peak attributed to two NHCS protons (δ 8.68 ppm), a singlet peak attributed to two OH protons of the thiosemicarbazone phenol rings (δ 8.98 ppm), and a singlet peak related to two =CH imine protons (δ 9.74 ppm).…”

Section: Characterizationsupporting

confidence: 89%

“…Literature procedures for the synthesis of p-tert-butylcalix [4]arene (1), 1,3 dinitrile-substituted p-tert-butylcalix [4]arene (2), 1,3 diamine-substituted p-tert-butylcalix [4]arene (3), and 1,3 diisocyanatesubstituted p-tert-butylcalix [4]arene (4) were followed [48,59,60]. Bisthiosemicarbazide-substituted p-tert-butylcalix [4]arene (5) was prepared as described in our recent paper [49].…”

Section: Preparation Of Ligandmentioning

confidence: 99%

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Synthesis, Crystal Structure, and Biological Activity of a Multidentate Calix[4]arene Ligand Doubly Functionalized by 2-Hydroxybenzeledene-Thiosemicarbazone

et al. 2020

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The design and synthesis of a novel tert-butyl-calix[4]arene functionalized at 1, 3 positions of the lower rim with two terminal 2-hydroxybenzeledene-thiosemicarbazone moieties is reported. The new ligand with multi-dentate chelating properties was fully characterized by several techniques: ESI-Mass spectroscopy, FT-IR, 1H-NMR, and single crystal X-ray diffraction. The solid state structure confirms that the calix[4]arene macrocycle has the expected open cone conformation, with two opposite phenyl rings inclined outwards with large angles. The conformation of the two alkoxythiosemicarbazone arms produces a molecule with a C2 point group symmetry. An interesting chiral helicity is observed, with the two thiosemicarbazone groups oriented in opposite directions like a two-blade propeller. A water molecule is encapsulated in the center of the two-blade propeller through multiple H-bond coordinations. The antibacterial, antifungal, anticancer, and cytotoxic activities of the calix[4]arene-thiosemicarbazone ligand and its metal derivatives (Co2+, Ni2+, Cu2+, and Zn2+) were investigated. A considerable antibacterial activity (in particular against E. coli, MIC, and MBC = 31.25 μg/mL) was observed for the ligand and its metal derivatives. Significant antifungal activities against yeast (C. albicans) were also observed for the ligand (MIC = 31.25 μg/mL and MBC = 125 μg/mL) and for its Co2+ derivative (MIC = 62.5 μg/mL). All compounds show cytotoxicity against the tested cancerous cells. For the Saos-2 cell line, the promising anticancer activity of ligand L (IC50 < 25 μg/mL) is higher than its metal derivatives. The microscopic analysis of DAPI-stained cells shows that the treated cells change in morphology, with deformation and fragmentation of the nuclei. The hemo-compatibility study demonstrated that this class of compounds are suitable candidates for further in vivo investigations.

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Section: Characterizationsupporting

confidence: 89%

Section: Characterizationsupporting

confidence: 89%

Section: Preparation Of Ligandmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Crystal Structure, and Biological Activity of a Multidentate Calix[4]arene Ligand Doubly Functionalized by 2-Hydroxybenzeledene-Thiosemicarbazone

et al. 2020

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“…p - tert -Butylcalix[4]arene 1 was synthesized using the method published by Gutsche et al (1981). Compound 2 (5,11,17,23-tetra- p - tert -butyl-25,27-bis[cianomethoxy]-26,28-dihyroxycalix[4]arene), compound 3 (5,11,17,23-tetra- p - tert -butyl-25,27-bis[aminoethoxy]-26,28-dihyroxycalix[4]arene), and compound 4 (5,11,17,23-tetra- p - tert -butyl-25,27-bis[2-isothiocyanoethoxy]-26,28-dihydroxycalix[4]arene) were synthesized using procedures reported by Collins et al (1991), Zhang and Huang (1997), and Quiroga-Campano et al (2017), respectively.…”

Section: Methodsmentioning

confidence: 99%

Design of a Thiosemicarbazide-Functionalized Calix[4]arene Ligand and Related Transition Metal Complexes: Synthesis, Characterization, and Biological Studies

et al. 2019

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In this study, we synthesized a new thiosemicarbazide-functionalized calix[4]arene L and its Co2+, Ni2+, Cu2+, and Zn2+ transition metal complexes. For characterization several techniques were employed: Fourier-transform infrared (FT-IR), 1H nuclear magnetic resonance (NMR), 13C-NMR, 15N-NMR, correlation spectroscopy (COZY), nuclear Overhauser enhancement spectroscopy (NOESY), electrospray ionization (ESI)–mass spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and elemental analysis. To explore the capability of the thiosemicarbazide function hosted on a calix[4]arene scaffold for growth inhibition of bacteria, fungi, and cancerous tumor cells, a series of biological evaluations were performed. For L, the antimicrobial tests revealed a higher antibacterial activity against gram-positive Bacillus subtilis and a lower activity against gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), whereas the gram-positive Staphylococcus aureus shows resistance. All examined metal derivatives show an enhancement of the antibacterial activity against gram-negative E. coli bacteria, with a more significant improvement for the Ni2+ and Zn2+ complexes. MTT assays showed a considerable in vitro anticancer activity of Co2+, Ni2+, and Cu2+ complexes against Saos-2 bone cancer cell lines. The activity is ascribable to the inorganic ions rather than calixarene ligand. Hemolysis assay results demonstrated that all compounds have high blood compatibility.

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“…Moreover, these compounds may host different molecules or ions within the hydrophobic cavity due to the interactions generated by the aromatic fraction 9 . Different types of guests, including neutral molecules 10,11 such as acetonitrile 12 , and various ions 13,14 , have been reported. The 5,11,17,23-Tetra-tert-butyl-25,27-bis(cyanomethoxy)-26,28-dihidroxycalix [4] arene (1) (dicyanocalix [4]arene) corresponds to p-tertbutylcalix [4]arene having a nitrile group 1,3-distal in its lower rim part 2 .…”

Section: Introductionmentioning

confidence: 99%

Nanodecoration of Single Crystals of 5,11,17,23-Tetra-Tert-Butyl-25,27-Bis(cyanomethoxy)-26, 28-Dihydroxycalix[4]arene

Moris

Silva

Saitz

et al. 2017

J. Chil. Chem. Soc.

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Single crystals of 1,3-bis(cyanomethoxy)calix [4]arene (1) were grown from Chloroform/Methanol mixture and these were nanodecorated with colloidal gold nanoparticles (AuNps). The single crystals were then characterized by single-crystal X-ray diffraction (XRD) and Scanning Electronic Microscopy (SEM). The nanodecorated crystals were characterized by UV-Visible Absorption Spectroscopy, Transmission Electronic Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). In this work, it is shown that the stabilization of the nanoparticles occurs through of the interactions of these with the nitrile group, maintaining their shape and size. . This supramolecular arrangement allows the attachment of gold nanoparticles (AuNPs) on the surface of a single crystal, maintaining their shape and size. KeywordsAs well as in cyclodextrin 17 and other supramolecular macrocycles 18 , nanodecoration of these compounds would allow the manufacturing of nanoscale devices with potential applications as sensors, switches and new materials having tunable properties 19,20 . In this work, we present the supramolecular analysis of dicyanocalix [4] arene, and the confirmation of the stabilization of nanoparticles by functional -CN group responsible for the formation of the crystal-nanodecoration. 2.MATERIAL AND METHODS Reagents and instrumentsAll the reagents used were of analytical reagent grade. p-tert-butylcalix [4] arene and gold chloride trihydrate (HAuCl 4 .3H 2 O) (Aldrich, >99%), Na 3 C 6 H 5 O 7 (Sigma-Aldrich), and nanopure water (Merck, Darmstadt, Germany). All Solvents employed for synthesis were commercially available and used as received without further purification. TEM was performed using a Zeiss model EM-109 microscope (Jena, Germany) operating at 80 kV (IBEC, Barcelona, Spain). SEM images were obtained using a high-resolution NOVA NanoSEM 230 instrument (FEI Company) equipped with an energy-dispersive detector.Single-Crystal XRD data were collected at room temperature using a Bruker Kappa CCD diffractometer with graphite-monochromatized MoKα radiation (λ=0.71073 Å). A Shimadzu UV-3101PC spectrophotometer (Shimadzu, Kyoto, Japan) was used. Spectra were recorded between 400 and 700 nm for colloidal nanoparticles. The diffuse reflectance results were converted into absorbance units using Kubelka-Munk conversion for de solid-state compounds.XPS spectra were recorded using a photoelectron spectrometer model 1257 (Perkin Elmer, Physical Electronic Division, Eden Prairie, MN, USA), fitted with an ultra-high-vacuum main chamber, a hemispherical electron analyzer, and an X-ray source that provided unfiltered Al Kα radiation. Energy calibration was accomplished by assigning a binding energy of 284.8 eV to the C 1s peak of adventitious carbon 21 . 5,11,17, Synthesis of arene (1)This compound is obtained as described by Zhang 2 . Single-crystals were obtained from a solution of (1) (0.6 mmol) in boiling chloroform (0.5 mL) with hot methanol added dropwise (1 mL). This solution was left for one week, at which point laminar c...

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Synthesis of bifunctional receptor for fluoride and cadmium based on calix[4]arene with thiourea moieties

Cited by 20 publications

References 27 publications

Synthesis, Crystal Structure, and Biological Activity of a Multidentate Calix[4]arene Ligand Doubly Functionalized by 2-Hydroxybenzeledene-Thiosemicarbazone

Synthesis, Crystal Structure, and Biological Activity of a Multidentate Calix[4]arene Ligand Doubly Functionalized by 2-Hydroxybenzeledene-Thiosemicarbazone

Design of a Thiosemicarbazide-Functionalized Calix[4]arene Ligand and Related Transition Metal Complexes: Synthesis, Characterization, and Biological Studies

Nanodecoration of Single Crystals of 5,11,17,23-Tetra-Tert-Butyl-25,27-Bis(cyanomethoxy)-26, 28-Dihydroxycalix[4]arene

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