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    Phosphorus-nitrogen compounds. Part 42. The comparative syntheses of 2-cis-4-ansa(N/O) and spiro(N/O) cyclotetraphosphazene derivatives: spectroscopic and crystallographic characterization, antituberculosis and cytotoxic activity studies
    (Royal Soc Chemistry, 2019) Binici, Arzu; Okumus, Aytug; Elmas, Gamze; Kilic, Zeynel; Ramazanoglu, Nagehan; Acik, Leyla; Simsek, Hulya
    The reaction of N4P4Cl8 (1) with one equimolar amount of the sodium salt of an N/O donor-type bidentate ligand (2) afforded two kinds of derivatives, namely, mono-ferrocenyl-2-cis-4-dichloro-ansa- (2,4-ansa; 3) and mono-ferrocenyl-spiro- (spiro; 4) hexachlorocyclotetraphosphazenes. The reaction yield (35%) of 4 was significantly larger than that of 3 (14%). The 2,4-ansa compound (3) was reacted with excess secondary amines to produce 2-cis-4-dichloro-ansa-cyclotetraphosphazenes (3a-3d). On the other hand, the spiro compound (4) gave fully substituted mono-ferrocenyl-spiro-cyclotetraphosphazenes (4a-4d) with excess monoamines as well. The tetrameric phosphazene derivatives were characterized by ESI-MS and/or HRMS, FTIR, HSQC, HMBC, H-1, C-13, and P-31 NMR spectroscopy and X-ray crystallography (for 4). It is observed that the 2,4-ansa and spiro-cyclotetraphosphazenes have different thermal stabilities. Additionally, the CVs of the new mono-ferrocenyl pendant-armed cyclotetraphosphazenes revealed electrochemically reversible one-electron oxidation of the Fe-redox centre. The 2,4-ansa phosphazenes (3 and 3a-3d) have two different stereogenic P centers indicating that they are expected to be in racemic mixtures (RR'/SS'). The chiralities of 3a and 3c were investigated by chiral HPLC. The manuscript also deals with the antimicrobial activities against G(+)/G(-) bacteria and fungi, the interactions with plasmid DNA, the in vitro cytotoxic activities against L929 fibroblast and MCF7 breast cells, and the antituberculosis activities against Mycobacterium tuberculosis H37Rv of the cyclotetraphosphazenes.
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    Phosphorus-nitrogen compounds. Part 65. Novel diansa-spiro-cyclotetraphosphazenes: synthesis, characterization, bioactivity and electrochemical properties, and dye-sensitized solar cell fabrication studies
    (Royal Soc Chemistry, 2022) Mutlu, Gurcu; Okumus, Aytug; Elmas, Gamze; Kilic, Zeynel; Guzel, Remziye; Sabah, Busra Nur; Acik, Leyla
    In this investigation, the substitution reaction of octachlorocyclotetraphosphazene, N4P4Cl8 (tetramer, OCCP, 1), with sodium 3-(N-ferrocenylmethylamino)-1-propanoxide (L1) was found to yield the compounds, 2,4-ansa-(2) and spiro-(2) cyclotetraphosphazene derivatives. The starting hexachloro-2-cis-4-dichloro-monoferrocenyl-ansa-(N/O)cyclotetraphosphazene (2) reacted separately with dipotassium salts of N2O2 donor-type aminopodands, (KOPhCH2NH)(2)R [R = (CH2)(n), n = 2 (L2) and n = 3 (L3)], to produce mono-ferrocenyl-2,4-ansa-6,8-ansa-spirocyclotetraphosphazenes (dias; 3 and 4). Both products were purified by column chromatography, and their structures were confirmed using ESIMS, FTIR, H-1, C-13, and P-31 NMR spectral data. Besides, the molecular and crystal structures of 4 were elucidated by single-crystal X-ray diffraction. Compound 4 has four-different chiral P-centers. However, the absolute configuration of stereogenic P-centres of an enantiomer was designated as SS'S '' R'''. Both new compounds were also used for the examination of optical and electrochemical properties, and survey of bioactivity. To this end, the minimum inhibitory, bactericidal, and fungicidal concentrations (MIC, MBC, and MFC) were determined with the microdilution technique. These MIC, MBC, and MFC values were found to vary between 2500 mu M and 312.5 mu M. DNA cleavage activities of 3 and 4 with pBR322 plasmid DNA were also studied using electrophoretic mobility on an agarose gel. BamHI and HindIII restriction enzyme digestions of compound-pBR322 plasmid DNA were conducted to supply more insight into changes in DNA conformation. Cyclotetraphosphazene 4 caused DNA cleavage activity even at the lowest concentration. In addition to that, compound 4 inhibited enzyme digestion, indicating that DNA binds to A/A nucleotides with DNA binding activity. Moreover, the cytotoxicities of 3 and 4 were investigated by MTT assay against MDA-MB-231 breast cancer cells and COS-1 mammalian fibroblast cells. On the other hand, the optical and electrochemical properties of dias 3 and 4 were studied using UV-vis absorption and cyclic voltammetry techniques. As a result, both compounds can be suggested as ferrocene-based charge transformable phosphazene structures that can be used as new generation and synergistic DSSC materials.
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    Phosphorus-nitrogen compounds. Part 72. Bisspiro(N/N) cyclotri-phosphazenes with 4-chlorobenzyl and ferrocenyl pendant arms: Synthesis, structural characterization, dye-sensitized solar cell fabrication and antituberculosis activity studies
    (Elsevier, 2024) Berberoglu, Ipek; Cemaloglu, Resit; Binici, Arzu; Yakut, Mehtap; Asmafiliz, Nuran; Kilic, Zeynel; Guzel, Remziye
    In this study, dichlorobisspiro(N/N)cyclotriphosphazenes with 4-chlorobenzyl and ferrocenyl-pendant arms were prepared to investigate their spectroscopic and crystallographic characterizations, and antituberculosis activities. The chlorine replacement reactions of tetrachloro(4-chlorobenzyl)spiro(N/N)cyclotri-phosphazenes with ferrocenyldiamines (4 and 5) lead to dichlorobispiro(N/N)cyclotriphosphazenes, containing unsymmetrical diaminospirorings. All cyclotriphosphazenes were characterized by mass spectrometry, FTIR and 31P NMR spectroscopies. Two different stereogenic P-centers are present in the unsymmetrically substituted inorganicorganic fused hybrid rings. These compounds may be in the form of racemic mixtures (RR'/SS' and RS'/SR'). The molecular and crystal structures of trans (6a and 7a) and cis (6b and 7b) isomers were elucidated by singlecrystal X-ray structural crystallography. The space groups of trans-6a, cis-6b, trans-7a and cis-7b are centrosymmetric P -1, P bca, P 21/n and P bca, respectively. Therefore, the crystal lattices contain both enantiomers. The absolute configurations of P2 atoms of 6a, 6b, 7a and 7b are R, R, S and S, respectively. It was determined that the most effective compound was 6b against Mycobacterium tuberculosis H37Rv (ATCC 27,294) strain among the phosphazenes 6a, 6b and 10b. Among the compounds, In the reversible cyclic voltammograms of ferrocenyldispirophosphazenes, only one oxidation-reduction wave was observed. The HOMO energy values of the compounds were figured out using the oxidation potential (Eox). Whereas, the LUMO energy values were figured out from the optical band gap values using Tauc plots. In addition, it was determined that the most effective compound that can be used in dye-sensitized solar cells (DSSCs) is cis-11b.
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    Phosphorus-nitrogen compounds: Part 60: Synthesis of hexaminomonoferrocenyl-spiro(N/O)cyclotetraphosphazenes: Spectral and electrochemical properties, tuning of redox feature, and antituberculosis activity
    (Taylor & Francis Ltd, 2023) Binici, Arzu; Elmas, Gamze; Okumus, Aytug; Guzel, Remziye; Simsek, Hulya; Kilic, Zeynel
    In the present investigation, the condensation reaction of octachlorocyclotetraphosphazene, N4P4Cl8 (1) (tetramer, OCCP), with sodium 3-(N-ferrocenylmethylamino)-1-propanoxide (L) resulted in the formation of the starting compound hexachloromonoferrocenylspiro(N/O)cyclotetraphosphazene (2). Thereafter, reactions of spiro (2) with excesses of 1-(2-aminoethyl)pyrrolidine, 1-(2-aminoethyl)piperidine and 4-(2-aminoethyl)morpholine in dry THF gave hexaaminomono-ferrocenylspiro(N/O)cyclotetraphosphazenes, 2a, 2b, and 2c, respectively. These new products were prepared for investigation of spectral and electrochemical properties, tuning of redox features, and examination of antituberculosis activities. The structures of 2a-2c were elucidated using elemental analysis, mass spectrometry (ESI-MS), FTIR, HMBC, HSQC, H-1, C-13 {H-1}, and P-31 {H-1} NMR data. The electrochemical behavior of these products containing monoferrocenyl group was investigated. Their use as potential alternative electrolyte redox couples for dye-sensitized solar cells (DSSC) was examined. The findings may inspire solar cell studies to explore the redox mediator behind the working mechanisms of DSSCs. Conversely, the antituberculosis activities of three compounds were examined against Mycobacterium tuberculosis H37Rv. The MIC values of 2a and 2 b were found to be as 30 and 35 mu g/mL, respectively, against the H37Rv reference strain.
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    Phosphorus-nitrogen compounds: part 71. Novel unsymmetrically-substituted dispiro-cyclotriphosphazenes: synthesis, characterization, antituberculosis activity, and phototunable charge storage studies
    (Royal Soc Chemistry, 2023) Cemaloglu, Resit; Berberoglu, Ipek; Yakut, Mehtap; Binici, Arzu; Asmafiliz, Nuran; Kilic, Zeynel; Guzel, Remziye
    The aim of this research is to synthesize and characterize new organic-inorganic hybrid multi-heterocyclic dichlorodispiro(N/N)cyclotriphosphazenes and to elucidate their antituberculosis activities. To achieve this aim, primarily, trans (6a-11a) and cis (6b-11b) unsymmetrical dichlorodispiro(N/N)cyclotriphosphazenes were obtained from ferrocenyldiamines (4 and 5) and benzyl-pendant armed tetrachloromonospirophosphazenes as starting materials. Several spectroscopic techniques (mass spectrometry, FTIR, and 1H, 13C, and 31P NMR), as well as elemental analysis, were employed to characterize the new phosphazenes. All unsymmetrically substituted phosphazenes are expected to be racemic mixtures (RR '/SS ' and RS '/SR ') due to two different stereogenic P-centers. In addition, the molecular and crystal structures of cis-6b, cis-10b, and cis-11b isomers were elucidated via single-crystal X-ray crystallography. They belong to centrosymmetric C2/c, P21/c, and P1 space groups, respectively; thus, their crystal lattices must contain both the enantiomers, RR '/SS ' or SR '/RS '. Moreover, only one oxidation-reduction wave was observed for the ferrocenyl-dispirophosphazenes in the reversible cyclic voltammograms. The HOMO and LUMO energy values of the phosphazenes were calculated using the oxidation potential (Eox) and the optical band gap values using Tauc plots, respectively. To determine the phototunable charge storage properties of the four dispirophosphazenes, their memory functions were investigated under UV illumination. The antituberculosis activities of the dichlorodispiro(N/N)cyclotriphosphazenes trans-6a, cis-6b, trans-10a, and cis-10b against Mycobacterium tuberculosis H37Rv (ATCC 27294) strain were evaluated. The results showed that among these compounds, trans-6a (MIC value 18 mu g mL-1) was much more effective than the other phosphazenes. Unsymmetrical cis/trans dispirocyclotriphosphazenes were prepared. The electrochemical behaviors and phototunable charge storage properties of the compounds were determined. The antituberculosis activities were examined against M. tuberculosis H37Rv.
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    spiro-Cyclotriphosphazenes containing 4-hydroxyphenylethyl pendant arm: Syntheses, structural characterization and DNA interaction study
    (Elsevier Science Sa, 2018) Pektas, Serhan; Kocak, Selen Bilge; Bosterzi, Nisan Sevin; Kilic, Zeynel; Zeyrek, Celal Tugrul; Coban, Burak; Yildiz, Ufuk
    The reaction of hexachlorocyclotriphosphazene, N3P3Cl6, with tyramine podand (2) afforded partly substituted spiro-cyclotriphosphazene (3). Amine-substituted spiro-cyclotriphosphazenes 4a-g were prepared by substitution of the Cl-atoms in 3 with pyrrolidine, piperidine, morpholine, 1,4-dioxa-8-azaspiro[4,5]decane, 1-(2-aminoethyl)pyrrolidine, 1-(2-aminoethyl) piperidine, and 4-(2-aminoethyl)-morpholine, respectively. All of the cyclotriphosphazene derivatives were characterized by elemental analysis, FTIR, MS, 1D H-1, C-13 and P-31 NMR and 2D HSQC techniques, and the crystal structures of 3 and 4b were verified by X-ray diffraction analysis. The relationships delta P-OPN shifts with exocyclic OPN (alpha') and endocyclic NPN (alpha) bond angles, and electron density transfer parameters Delta(P-N) for spiro-cyclotriphosphazenes were presented. The DNA cleavage activity of cyclotriphosphazene derivatives (3, and 4a-g) was studied on double-stranded pBR322 DNA using gel electrophoresis experiments. It was found that 4e and 4f caused the highest level of DNA damage. The interactions of 3 and 4e with calf thymus DNA were also investigated using absorption spectrometry. The molecular docking was performed to identify the interaction of the compounds (3 and 4b) with the DNA (PDB ID:3V9D for A-DNA and PDB ID:1BNA for B-DNA). (C) 2018 Elsevier B.V. All rights reserved.
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    Syntheses, structural characterization and biological activities of spiro-ansa-spiro-cyclotriphosphazenes
    (Royal Soc Chemistry, 2015) Basterzi, Nisan Sevin; Kocak, Selen Bilge; Okumus, Aytug; Kilic, Zeynel; Hokelek, Tuncer; Celik, Omer; Turk, Mustafa
    The replacement reactions of the Cl-atoms in partly substituted spiro-ansa-spiro-cyclotriphosphazenes (7 and 8) with excess pyrrolidine, 4-(2-aminoethyl) morpholine, and 1,4-dioxa-8-azaspiro[4,5] decane in dry THF led to the formation of heterocyclic amine substituted cyclotriphosphazenes (9a-c and 10a-c). All cyclotriphosphazene derivatives were characterized by elemental analysis, FTIR, MS, 1D H-1, C-13 and P-31 NMR and 2D HSQC, and HMBC techniques, and the crystal structure of partly substituted cyclotriphosphazene 8 was verified by X-ray diffraction analysis. Cyclotriphosphazene derivatives (5-8, 9a-c, and 10a-c) were subjected to antimicrobial activity against seven clinic bacteria and one yeast strain, and the interactions of the phosphazenes with plasmid pBR322 DNA were investigated. Phosphazene derivatives [(5, 7, 8, 9b and 9c) and (10a and 10b)] caused a slight increase and substantial decrease in the mobility of form I DNA, respectively, while 9a caused retardation on gel. Cytotoxic, apoptotic and necrotic effects against L929 fibroblast and A549 lung cancer cells were also evaluated. While the highest toxic effect was obtained for 9a in L929 fibroblast cells and for 9c in A549 lung cancer cells at 100 mg mL(-1) concentration, the highest apoptotic effect was determined for 10a in L929 fibroblast cells and for 9a in A549 lung cancer cells at the same concentration. It was found that 9a and 10b exhibited the most necrotic effects against L929 fibroblast and A549 lung cancer cells, respectively. The toxic and necrotic effects of the phosphazenes against A549 lung cancer cells were greater than those against L929 fibroblast cells, whereas, the apoptotic effect of the compounds was greater in L929 fibroblast cells than in A549 lung cancer cells.