Metalo components exhibiting significant anticancer and antibacterial properties: a novel sandwich-type like polymeric structure.

Four new dicyanoargentate(I)-based complexes 1-4 were synthesized from certain metal ions with a tetradentate ligand [N, N-bis (2-hydroxyethyl) -ethylenediamine; N-bishydeten] and determined by diverse procedures (elemental, thermal, FT-IR, ESI-MS for 1-3 and, magnetic susceptibility and EPR for 1, and 2) including crystal analysis of 4. The crystal method revealed that complex 4 has a sandwich-type like polymeric chemical structure with layers formed by [Cd(N-bishydeten)2]2+ cations and [Ag(CN)2]- anions. The complexes were further characterized by fluorescence and UV spectroscopy to determine their physicochemical features. The complexes displayed a DNA binding activity within the same range as found for cisplatin, in addition to their strong stability in the presence of the physiological buffer system. The complexes were also investigated for pharmacological properties like interaction with DNA/Bovine serum albumin, anticancer and antibacterial activities. Physicochemical studies of DNA with the complexes suggested that the interaction mode between them are possibly both intercalative and groove binding types. These spectroscopic measurements also show that there may be a binding tendency between BSA and the complexes via hydrogen or Van der Waals bonds. The viability tests demonstrated that all the complexes exhibited antibacterial (1-4) and anticancer effects (2-4) toward ten diverse bacterial strains and three tumor cells (HT-29 colon adenocarcinoma, HeLa cervical cancer, and C6 glioma), respectively.

Synthesis and characterization of trimeric phosphazene based ionic liquids with tetrafluoroborate anions and their thermal investigations.

The quaternized compounds (PzIL1-9) reacted with sodium tetrafluoroborate (NaBF4) to generate phosphazene based ionic liquids (PzILs), PzIL1a-9a. The newly synthesized ionic compounds (PzIL1a-9a) were verified using elemental CHN analyses and functional and spectroscopic (FTIR and 1H, 13C, 31P-NMR) analyses techniques. The thermal properties of PzIL1a-9a were investigated using thermogravimetric analysis (TGA). According to the initial decomposition temperature values calculated based on the TGA thermograms, PzIL7a (213 °C) was recognized to be more thermally stable than the other PzILs studied. PzIL1a-9a exhibited good solubility in the water and demonstrate a typical dielectric relaxation behavior, conductivity levels for both low and high-frequency regions. AC conductivity mechanisms and dielectric relaxation behavior of each sample are investigated by fabricating parallel plate capacitors.

Synthetic Access to a Pure Polyradical Architecture: Nucleophilic Insertion of Nitronyl Nitroxide on a Cyclotriphosphazene Scaffold.

An optimized nucleophilic synthetic approach featuring mild conditions and microwave energy was utilized to circumvent the classical Ullman procedure and access a polynitronyl nitroxide radical easily and in pure form. The simultaneous controlled introduction of preformed nitronyl nitroxide radicals on a cyclotriphosphazene core leads to a novel polyphosphazene monomer which is suitable for both n- and a p-type redox-active material in organic rechargeable batteries as demonstrated by electrochemistry. Additionally, absorption spectra and square-wave voltammetry were utilized to quantify the number of nitronyl nitroxide radical units on the cyclotriphosphazene scaffold.

Synthesis and crystal structures of novel copper(II) complexes with glycine and substituted phenanthrolines: reactivity towards DNA/BSA and in vitro cytotoxic and antimicrobial evaluation.

New copper(II) complexes-dimeric-[Cu(nphen)(gly)(H2O)]+ (1) and [Cu(dmphen)(gly)(NO3)(H2O)] (2) (nphen = 5-nitro-1,10-phenanthroline, dmphen = 4,7-dimethyl-1,10-phenanthroline, and gly = glycine)-have been synthesized and characterized by CHN analysis, single-crystal X-ray diffraction techniques, FTIR, EPR spectroscopy, and cyclic voltammetry. The CT-DNA-binding properties of these complexes have been investigated by thermal denaturation measurements and both absorption and emission spectroscopy. The DNA cleavage activity of these complexes has been studied on supercoiled pUC19 plasmid DNA by gel electrophoresis experiments in the absence and presence of H2O2. Furthermore, the interaction of these complexes with bovine serum albumin (BSA) has been investigated using absorption and emission spectroscopy. The thermodynamic parameters, free-energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS) for BSA + complexes 1 and 2 systems have been calculated by the van't Hoff equation at three different temperatures (293.2, 303.2, and 310.2 K). The distance between the BSA and these complexes has been determined using fluorescence resonance energy transfer (FRET). Conformational changes of BSA have been observed using the synchronous fluorescence technique. In addition, in vitro cytotoxicities of these complexes on tumor cell lines (Caco-2, A549, and MCF-7) and healthy cells (BEAS-2B) have been examined. The antimicrobial activity of the complexes has also been tested on certain bacteria cells. The effect of mono and dimeric in the above complexes is presented and discussed. New copper(II) complexes-dimeric-[Cu(nphen)(gly)(H2O)]+ (1) and [Cu(dmphen)(gly) (NO3)(H2O)] (2) (nphen = 5-nitro-1,10-phenanthroline, dmphen = 4,7-dimethyl-1,10-phenanthroline and gly = glycine)-have been synthesized and characterized by CHN analysis, single-crystal X-ray diffraction techniques, FTIR and EPR spectroscopy. They have been tested for their in vitro DNA/BSA interactions by the spectroscopic methods. These complexes exhibited higher cytotoxic and antimicrobial activities. Complex 1 shows better DNA / BSA interactions in comparison to complex 2.

Synthesis and Straightforward Quantification Methods of Imino Nitroxide-Based Hexaradical Architecture on a Cyclotriphosphazene Scaffold.

The synthesis of a homogeneous neutral hexaradical architecture consisting of six imino nitroxide radical moieties covalently bonded on a cyclotriphosphazene scaffold was reported. The synthesis of hexaradical imino nitroxide compounds follows the Ullman procedure involving the condensation of 2,3-bis(hydroxylamino)-2,3-dimethylbutane with hexa-(4-formylphenoxy)cyclotriphosphazene (3) followed by oxidation of the condensation product hexa-[4-(1-hydroxy-4,4,5,5-tetramethyl-2-imidazoline-2-yl)phenoxy]cyclotriphosphazene (2) by NaIO4. Characterization of hexaradical was performed by X-ray and SQUID in solid state and by EPR, absorption spectroscopy, and electrochemistry in solution. CV of 1 shows an oxidation peak at 1.184 V (vs SCE) and a reduction peak at -0.883 V, both characteristics of the presence of phenyl imino nitroxide (7) moieties, suggesting that the contribution of the cyclotriphosphazene core is negligible. Attention was particularly focused on developing methods, UV-vis spectroscopy and square-wave voltammetry, to quantify the number of radicals in a way to confirm easily and rapidly the polyradicals' structure.

TEMPO-functionalized zinc phthalocyanine: synthesis, magnetic properties, and its utility for electrochemical sensing of ascorbic acid.

Zinc(ii) phthalocyanine (TEMPO-ZnPc), peripherally functionalized with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radicals is synthesized and its magneto structural and electrochemical behaviors are investigated. TEMPO-ZnPc shows multi-electron ring based reduction reactions and a TEMPO based oxidation reaction. Spectroelectrochemical measurements support these peak assignments. TEMPO-ZnPc is tested as a homogeneous and heterogeneous ascorbic acid (AA) sensor. Disappearance of TEMPO-ZnPc based reduction processes and the observation of new waves at around 0 and 1.20 V with respect to increasing AA concentration indicate the interaction of TEMPO-ZnPc with AA and usability of the complex as an electrochemical AA sensor. For practical usage as heterogeneous electrocatalysts for AA sensing, a glassy carbon electrode (GCE) is coated with TEMPO-ZnPc (GCE/TEMPO-ZnPc) and this modified electrode is tested as a heterogeneous AA sensor. The redox peak of GCE/TEMPO-ZnPc at 0.81 V decreases the peak current while a new wave is observed at 0.65 V during the titration of the electrolyte with AA. GCE/TEMPO-ZnPc sense AA with 1.75 × 10(-6) mol dm(-3) LOD with a sensitivity of 1.89 × 10(3) A cm mol(-1).

Design of a Gd-DOTA-phthalocyanine conjugate combining MRI contrast imaging and photosensitization properties as a potential molecular theranostic.

The design and synthesis of a phthalocyanine--Gd-DOTA conjugate is presented to open the way to novel molecular theranostics, combining the properties of MRI contrast imaging with photodynamic therapy. The rational design of the conjugate integrates isomeric purity of the phthalocyanine core substitution, suitable biocompatibility with the use of polyoxo water-solubilizing substituents, and a convergent synthetic strategy ended by the use of click chemistry to graft the Gd-DOTA moiety to the phthalocyanine. Photophysical and photochemical properties, contrast imaging experiments and preliminary in vitro investigations proved that such a combination is relevant and lead to a new type of potential theranostic agent.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 µ(B) per Cu(II)) and 6 (2.79 µ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed.

Crystal structure and EPR studies of doped Cu(2+) ion in [Zn(sac)(2)(en)(2)] single crystal.

The tran-bis(ethylenediamine)bis(saccharinato)Zinc(II), [Zn(sac)(2)(en)(2)] (ZSED), (en: ethylenediamine and sac: saccharinate) complex has been synthesized and its crystal structure has been determined by X-ray diffraction analysis. The compound crystallizes in space group P2(1)/c. The Zn(II) ion is hexa-coordinated by four nitrogens of two bidentate en ligands composing the basal plane and two nitrogen atoms from the monodentate two sac ligands (N-bonded) occuping the axial sites, adopting an elongated octahedral sphere. Both en and sac ligands occupy the trans positions of the coordination octahedron. The Zn(II) ion in title compound sits on a inversion centre and is octahedrally coordinated two bidentate en (ethylenediamine) and two sac (saccharinate) (N-bonded) ligands. The magnetic environments of Cu(2+) doped [Zn(sac)(2)(en)(2)] complex have been identified by electron paramagnetic resonance (EPR) technique. Cu(2+) doped ZSED single crystals have been studied at room temperature in three mutually perpendicular planes. The calculated results of the Cu(2+) doped ZSED indicate that Cu(2+) ion contains two magnetically inequivalent Cu(2+) sites in distinct orientations occupying substitutional positions in the host lattice and show very high angular dependence.

Effect of substituents on spin density in benzimidazole nitronyl nitroxide radicals studied by electron spin resonance.

Several novel benzimidazole-3-oxide-1-oxyl radicals with substituents at 5 and/or 6 position were synthesized. The ESR analysis of nitrogen hyperfine coupling constants (hfccs) revealed that substituents at 5 and 6-position affect the spin density to greater extent than substituents on the phenyl ring at 2-position. Density functional theory calculations of nitrogen hfccs were performed using several different Pople type basis sets, as well as double and triple zeta quality individual gauge for localized orbital (IGLO-II, IGLO-III) and electron paramagnetic resonance (EPR-II, EPR-II) basis sets. Experimental and theoretical hfccs are compared.