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16 pages, 14076 KiB

Open AccessArticle

DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-a:2′,3′-c]phenazine (dppz) Ligands: Synthesis, Crystal Structures, Stability, Luminescence Properties and CT-DNA Interaction

by Aleksandar Savić, Anna M. Kaczmarek, Rik Van Deun and Kristof Van Hecke

Molecules 2020, 25(22), 5309; https://doi.org/10.3390/molecules25225309 - 13 Nov 2020

Cited by 6 | Viewed by 2569

Abstract

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO₃)₃(dppz)₂] (Ln = Nd³⁺, Er³⁺ and Yb³⁺; dppz = dipyrido[3,2-a:2′,3′-c [...] Read more.

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO₃)₃(dppz)₂] (Ln = Nd³⁺, Er³⁺ and Yb³⁺; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce³⁺, Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Tm³⁺, Lu³⁺) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analysis of the complexes (Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Eu³⁺, Er³⁺, Yb³⁺, Lu³⁺) showed that the lanthanide’s first coordination sphere can be described as a bicapped dodecahedron, made up of two bidentate dppz ligands and three bidentate-coordinating nitrate anions. Efficient energy transfer was observed from the dppz ligand to the lanthanide ion (Nd³⁺, Er³⁺ and Yb³⁺), while relatively high luminescence lifetimes were detected for these complexes. In their excitation spectra, the maximum of the strong broad band is located at around 385 nm and this wavelength was further used for excitation of the chosen complexes. In their emission spectra, the following characteristic NIR emission peaks were observed: for a) Nd³⁺: ⁴F_3/2 → ⁴I_9/2 (870.8 nm), ⁴F_3/2 → ⁴I_11/2 (1052.7 nm) and ⁴F_3/2 → ⁴I_13/2 (1334.5 nm); b) Er³⁺: ⁴I_13/2 → ⁴I_15/2 (1529.0 nm) c) Yb³⁺: ²F_5/2 → ²F_7/2 (977.6 nm). While its low triplet energy level is ideally suited for efficient sensitization of Nd³⁺ and Er³⁺, the dppz ligand is considered not favorable as a sensitizer for most of the visible emitting lanthanide ions, due to its low-lying triplet level, which is too low for the accepting levels of most visible emitting lanthanides. Furthermore, the DNA intercalation ability of the [Nd(NO₃)₃(dppz)₂] complex with calf thymus DNA (CT-DNA) was confirmed using fluorescence spectroscopy. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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13 pages, 2223 KiB

Open AccessArticle

Characterization of Ciprofloxacin-Bismuth-Loaded Antibacterial Wound Dressing

by Dorota Kowalczuk, Małgorzata Miazga-Karska, Agata Gładysz, Paweł Warda, Agnieszka Barańska and Bartłomiej Drop

Molecules 2020, 25(21), 5096; https://doi.org/10.3390/molecules25215096 - 03 Nov 2020

Cited by 17 | Viewed by 3025

Abstract

The research was focused on developing a potentially antibacterial wound dressing made of polyurethane foam and loaded with bismuth-ciprofloxacin (Cip-Bi). The Cip-Bi chemical structure was confirmed by Fourier transform infrared spectroscopic (FTIR) analysis. The sought after antibacterial wound dressing was obtained by modification [...] Read more.

The research was focused on developing a potentially antibacterial wound dressing made of polyurethane foam and loaded with bismuth-ciprofloxacin (Cip-Bi). The Cip-Bi chemical structure was confirmed by Fourier transform infrared spectroscopic (FTIR) analysis. The sought after antibacterial wound dressing was obtained by modification of the raw dressing with an iodine or bromine solution and subsequently with a Cip-Bi hydrogel. The amount of Cip-Bi loaded into the dressing matrix was determined indirectly on the basis of the differences in Cip-Bi concentrations, before and after the modification process, and the determination was performed with the HPLC (high-performance liquid chromatography) method. The modified dressing was found to have a two-step release of Cip-Bi, a feature helpful in the treatment of locally infected wounds and prevention of secondary bacterial infection. The zone of inhibition test against the selected Gram-positive and Gram-negative bacteria confirmed the antibacterial activity of the Cip-Bi-modified dressing. Preliminary tests conducted so far have been indicative of the Cip-Bi dressing’s relatively high activity against the tested organisms. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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23 pages, 5764 KiB

Open AccessArticle

Synthesis, Crystal Structure, and Computational Methods of Vanadium and Copper Compounds as Potential Drugs for Cancer Treatment

by Nidia D. Corona-Motolinia, Beatriz Martínez-Valencia, Lisset Noriega, Brenda L. Sánchez-Gaytán, Miguel Ángel Méndez-Rojas, Francisco J. Melendez, María Eugenia Castro and Enrique González-Vergara

Molecules 2020, 25(20), 4679; https://doi.org/10.3390/molecules25204679 - 14 Oct 2020

Cited by 11 | Viewed by 2983

Abstract

Transition metal-based compounds have shown promising uses as therapeutic agents. Among their unique characteristics, these compounds are suitable for interaction with specific biological targets, making them important potential drugs to treat various diseases. Copper compounds, of which Casiopeinas^® are an excellent example, [...] Read more.

Transition metal-based compounds have shown promising uses as therapeutic agents. Among their unique characteristics, these compounds are suitable for interaction with specific biological targets, making them important potential drugs to treat various diseases. Copper compounds, of which Casiopeinas^® are an excellent example, have shown promising results as alternatives to current cancer therapies, in part because of their intercalative properties with DNA. Vanadium compounds have been extensively studied for their pharmacological properties and application, mostly in diabetes, although recently, there is a growing interest in testing their activity as anti-cancer agents. In the present work, two compounds, [Cu(Metf)(bipy)Cl]Cl·2H₂O and [Cu(Impy)(Gly)(H₂O)]VO₃, were obtained and characterized by visible and FTIR spectroscopies, single-crystal X-ray diffraction, and theoretical methods. The structural and electronic properties of the compounds were calculated through the density functional theory (DFT) using the Austin–Frisch–Petersson functional with dispersion APFD, and the 6-311 + G(2d,p) basis set. Non-covalent interactions were analyzed using Hirshfeld surface analysis (HSA) and atom in molecules analysis (AIM). Additionally, docking analysis to test DNA/RNA interactions with the Casiopeina-like complexes were carried out. The compounds provide metals that can interact with critical biological targets. In addition, they show interesting non-covalent interactions that are responsible for their supramolecular arrangements. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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23 pages, 2183 KiB

Open AccessArticle

Design of Organoiron Dendrimers Containing Paracetamol for Enhanced Antibacterial Efficacy

by Alaa S. Abd-El-Aziz, Ebtehal G. El-Ghezlani and Amani A. Abdelghani

Molecules 2020, 25(19), 4514; https://doi.org/10.3390/molecules25194514 - 02 Oct 2020

Cited by 6 | Viewed by 2208

Abstract

Paracetamol (acetaminophen) is a common painkiller and antipyretic drug used globally. Attachment of paracetamol to a series of organoiron dendrimers was successfully synthesized. The aim of this study is to combine the benefits of the presence of these redox-active organoiron dendrimers, their antimicrobial [...] Read more.

Paracetamol (acetaminophen) is a common painkiller and antipyretic drug used globally. Attachment of paracetamol to a series of organoiron dendrimers was successfully synthesized. The aim of this study is to combine the benefits of the presence of these redox-active organoiron dendrimers, their antimicrobial activities against some human pathogenic Gram-positive, and the therapeutic characteristics of paracetamol. The antimicrobial activity of these dendrimers was investigated and tested with a minimum inhibitory concentration and this has been reported. Some of these newly synthesized dendrimers exhibited the highest inhibitory activity against methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus faecium (VRE), and Staphylococcus warneri compared to reference drugs. The results of this study indicate that the antimicrobial efficacy of the dendrimers is dependent on the size of the redox-active organoiron dendrimer and its terminal functionalities. The best result has been recorded for the fourth-generation dendrimer 11, which attached to 48 paracetamol end groups and has 90 units composed of the η⁶-aryl-η⁵-cyclopentadienyliron (II) complex. This dendrimer presented inhibition of 50% of the growth (IC₅₀) of 0.52 μM for MRSA, 1.02 μM for VRE, and 0.73 μM for Staphylococcus warneri. The structures of the dendrimers were characterized by elemental analysis, Fourier transform infrared (FT-IR), nuclear magnetic resonance (¹H-NMR), and ¹³C-NMR spectroscopic techniques. In addition, all synthesized dendrimers displayed good thermal stability in the range of 300–350 °C following the degradation of the cationic iron moieties which occurred around 200 °C. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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13 pages, 1179 KiB

Open AccessFeature PaperArticle

Antiviral, Antibacterial, Antifungal, and Cytotoxic Silver(I) BioMOF Assembled from 1,3,5-Triaza-7-Phoshaadamantane and Pyromellitic Acid

by Sabina W. Jaros, Jarosław Król, Barbara Bażanów, Dominik Poradowski, Aleksander Chrószcz, Dmytro S. Nesterov, Alexander M. Kirillov and Piotr Smoleński

Molecules 2020, 25(9), 2119; https://doi.org/10.3390/molecules25092119 - 01 May 2020

Cited by 42 | Viewed by 3771

Abstract

The present study reports the synthesis, characterization, and crystal structure of a novel bioactive metal-organic framework, [Ag₄(µ-PTA)₂(µ₃-PTA)₂(µ₄-pma)(H₂O)₂]_n·6nH₂O (bioMOF 1), which [...] Read more.

The present study reports the synthesis, characterization, and crystal structure of a novel bioactive metal-organic framework, [Ag₄(µ-PTA)₂(µ₃-PTA)₂(µ₄-pma)(H₂O)₂]_n·6nH₂O (bioMOF 1), which was assembled from silver(I) oxide, 1,3,5-triaza-7-phosphaadamantane (PTA), and pyromellitic acid (H₄pma). This product was isolated as a stable microcrystalline solid and characterized by standard methods, including elemental analysis, ¹H and ³¹P{¹H} NMR and FTIR spectroscopy, and single crystal X-ray diffraction. The crystal structure of 1 disclosed a very complex ribbon-pillared 3D metal-organic framework driven by three different types of bridging ligands (µ-PTA, µ₃-PTA, and µ₄-pma⁴⁻). Various bioactivity characteristics of bioMOF 1 were investigated, revealing that this compound acts as a potent antimicrobial against pathogenic strains of standard Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria, as well as a yeast (Candida albicans). Further, 1 showed significant antiviral activity against human adenovirus 36 (HAdV-36). Finally, bioMOF 1 revealed high cytotoxicity toward an abnormal epithelioid cervix carcinoma (HeLa) cell line with low toxicity toward a normal human dermal fibroblast (NHDF) cell line. This study not only broadens the family of PTA-based coordination polymers but also highlights their promising multifaceted bioactivity. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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15 pages, 2017 KiB

Open AccessArticle

DNA-Binding and Anticancer Activity of Binuclear Gold(I) Alkynyl Complexes with a Phenanthrenyl Bridging Ligand

by Mona S. Alsaeedi, Bandar A. Babgi, Mostafa A. Hussien, Magda H. Abdellattif and Mark G. Humphrey

Molecules 2020, 25(5), 1033; https://doi.org/10.3390/molecules25051033 - 25 Feb 2020

Cited by 22 | Viewed by 3992

Abstract

3,6-Diethynyl-9,10-diethoxyphenanthrene (4) was synthesized from phenanthrene and employed in the synthesis of the binuclear gold(I) alkynyl complexes (R₃P)Au(C≡C–3-[C₁₄H₆-9,10-diethoxy]-6–C≡C)Au(PR₃) (R = Ph (5a), Cy (5b)). The diyne 4 and complexes [...] Read more.

3,6-Diethynyl-9,10-diethoxyphenanthrene (4) was synthesized from phenanthrene and employed in the synthesis of the binuclear gold(I) alkynyl complexes (R₃P)Au(C≡C–3-[C₁₄H₆-9,10-diethoxy]-6–C≡C)Au(PR₃) (R = Ph (5a), Cy (5b)). The diyne 4 and complexes 5a and 5b were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. UV-Vis spectroscopy studies of the metal complexes and precursor diyne show strong π → π* transitions in the near UV region that red shift by ca. 50 nm upon coordination at the gold centers. The emission spectrum of 4 shows an intense fluorescence band centered at 420 nm which red shifts, slightly upon coordination of 4 to gold. Binding studies of 4, 5a, and 5b against calf thymus DNA were carried out, revealing that 4, 5a, and 5b have ≥40% stronger binding affinities than the commonly used intercalating agent ethidium bromide. The molecular docking scores of 4, 5a, and 5b with B-DNA suggest a similar trend in behavior to that observed in the DNA-binding study. Unlike the ligand 4, promising anticancer properties for 5a and 5b were observed against several cell lines; the DNA binding capability of the precursor alkyne was maintained, and its anticancer efficacy enhanced by the gold centers. Such phenanthrenyl complexes could be promising candidates in certain biological applications because the two components (phenanthrenyl bridge and metal centers) can be altered independently to improve the targeting of the complex, as well as the biological and physicochemical properties. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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20 pages, 5727 KiB

Open AccessArticle

Biological and Spectroscopic Investigations of New Tenoxicam and 1.10-Phenthroline Metal Complexes

by Hazem S. Elshafie, Sadeek A. Sadeek, Ippolito Camele, Hanem M. Awad and Amira A. Mohamed

Molecules 2020, 25(5), 1027; https://doi.org/10.3390/molecules25051027 - 25 Feb 2020

Cited by 17 | Viewed by 2797

Abstract

In the present work, tenoxicam (H₂Ten) reacted with Mn(II), Co(II), Ni(II), Cu(II) and Zn (II) ions in the presence of 1.10-phenthroline (Phen), forming new mixed ligand metal complexes. The properties of the formed complexes were depicted by elemental analyses, infrared, electronic [...] Read more.

In the present work, tenoxicam (H₂Ten) reacted with Mn(II), Co(II), Ni(II), Cu(II) and Zn (II) ions in the presence of 1.10-phenthroline (Phen), forming new mixed ligand metal complexes. The properties of the formed complexes were depicted by elemental analyses, infrared, electronic spectra, proton nuclear magnetic resonance (¹H NMR), mass spectrometry, thermogravimetric (TGA) and differential thermogravimetric (DTG) analysis, molar conductance and magnetic moment. IR spectra demonstrated that H₂Ten acted as a neutral bidentate ligand, coordinated to the metal ions via the pyridine-N and carbonyl group of the amide moiety, and Phen through the nitrogen atoms. Kinetic thermodynamics parameters activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*), Gibbs, free energy (ΔG*) associated to the complexes have been evaluated. Antibacterial screening of the compounds was carried out in vitro against Clavibacter michiganensis, Xanthomonas campestris and Bacillus megaterium. Antifungal activity was performed in vitro against Monilinia fructicola, Penicillium digitatum and Colletotrichum acutatum. The possible phytotoxic effect of the studied compounds was also investigated on Solanum lycopersicum (tomatoes) and Lepidium sativum (garden cress) seeds. The anticancer activity was screened against cell cultures of HCT-116 (human colorectal carcinoma), HepG2 (human hepatocellular carcinoma) and MCF-7 (human breast adenocarcinoma). Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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Review

Jump to: Research

22 pages, 4603 KiB

Open AccessReview

Chemistry and Some Biological Potential of Bismuth and Antimony Dithiocarbamate Complexes

by Jerry O. Adeyemi and Damian C. Onwudiwe

Molecules 2020, 25(2), 305; https://doi.org/10.3390/molecules25020305 - 12 Jan 2020

Cited by 39 | Viewed by 5093

Abstract

Interest in the synthesis of Bi(III) and Sb(III) dithiocarbamate complexes is on the rise, and this has been attributed to their wide structural diversity and their interesting application as biological agents and in solid state/materials chemistry. The readily available binding sites of the [...] Read more.

Interest in the synthesis of Bi(III) and Sb(III) dithiocarbamate complexes is on the rise, and this has been attributed to their wide structural diversity and their interesting application as biological agents and in solid state/materials chemistry. The readily available binding sites of the two sulphur atoms within the dithiocarbamate moiety in the complexes confers a wide variety of geometry and interactions that often leads to supramolecular assemblies. Although none of the bismuth or antimony metals are known to play any natural biological function, their dithiocarbamate complexes, however, have proven very useful as antibacterial, antileishmanial, anticancer, and antifungal agents. The dithiocarbamate ligands modulate the associated toxicity of the metals, especially antimony, since bismuth is known to be benign, allowing the metal ion to get to the targeted sites; hence, making it less available for side and other damaging reactions. This review presents a concise chemistry and some known biological potentials of their trivalent dithiocarbamate complexes. Full article

(This article belongs to the Special Issue Metal Coordination Complexes for Biomedical Applications)

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