Synthesis and Characterization of Ru(II) Complexes with π-Expansive Imidazophen Ligands for the Photokilling of Human Melanoma Cells

Ru(II) complexes were synthesized with π-expanding (phenyl, fluorenyl, phenanthrenyl, naphthalen-1-yl, naphthalene-2-yl, anthryl and pyrenyl groups) attached at a 1H-imidazo[4,5-f][1,10]phenanthroline ligand and 4,4′-dimethyl-2,2′-bipyridine (4,4′-dmb) coligands. These Ru(II) complexes were characterized by 1D and 2D NMR, and mass spectroscopy, and studied for visible light and dark toxicity to human malignant melanoma SK-MEL-28 cells. In the SK-MEL-28 cells, the Ru(II) complexes are highly phototoxic (EC₅₀ = 0.2–0.5 µm ) and have low dark toxicity (EC₅₀ = 58–230 µm ). The highest phototherapeutic index (PI) of the series was found with the Ru(II) complex bearing the 2-(pyren-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand. This high PI is in part attributed to the π-rich character added by the pyrenyl group, and a possible low-lying and longer-lived ³IL state due to equilibration with the ³MLCT state. While this pyrenyl Ru(II) complex possessed a relatively high quantum yield for singlet oxygen formation (Φ_∆ = 0.84), contributions from type-I processes (oxygen radicals and radical ions) are competitive with the type-II (¹O₂) process based on effects of added sodium azide and solvent deuteration.     

Simultaneous parallel and antiparallel self-assembly in a triazole/amide macrocycle conformationally homologous to D-,L-α-amino acid based cyclic peptides: NMR and molecular modeling study

A 1,4-linked triazole/amide based peptidomimetic macrocycle, synthesized from a triazole amide oligomer of cis-furanoid sugar triazole amino acids, possesses a conformation resembling the D-,L-α-amino acid based cyclic peptides despite having uniform backbone chirality. It undergoes a unique mode of self-assembly through an antiparallel backbone to backbone intermolecular H-bonding involving amide NH and triazole N2/N3 as well as parallel stacking via amide NH and carbonyl oxygen H-bonding, leading to the formation of a tubular nanostructure.     

Separation of isomers of sulfophthalic acid by guest induced host framework formation with 4,4'-bipyridine

The selective inclusion of aromatic guest molecules in host frameworks formed by 3-sulfophthalic acid or 4-sulfophthalic acid and 4,4'-bipyridine has been effectively utilized for the separation of sulfophthalic acid isomers.     

Role of anions in the synthesis of cyclobutane derivatives via [2 + 2] cycloaddition reaction in the solid state and their isomerization in solution

trans-3-(4'-Pyridyl)acrylic acid (4-PA) is inert to photodimerization reaction both in solution and solid state. It is made photoreactive by forming salts with various acids. The anions of these salts play a key role in directing the packing of 4-PAH(+) in the solid state. The anions CF(3)CO(2)(-), Cl(-), ClO(4)(-), and BF(4)(-) direct the parallel alignments of 4-PAH(+) in head-to-tail (HT) fashion and lead to the formation of HT-photodimer. On the other hand, bivalent anion SO(4)(2-) directs parallel alignment of 4-PAH(+) in head-to-head (HH) fashion and lead to the formation of HH-photodimer. The details of the anion-controlled stereoselective syntheses of these two cyclobutane derivatives are presented. Interestingly, both cyclobutane compounds undergo isomerization from rctt-form to rctc-form in solution catalyzed by acid.     

Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> alloy nanoparticles embedded SiO<Subscript>2</Subscript> films: synthesis and structure

Cu–Ni fcc alloy nanoparticles (NPs) of tunable atomic ratios were generated in SiO₂ films. The films were prepared using the Cu(NO₃)₂ and Ni(NO₃)₂ co-doped inorganic–organic hybrid silica sols by single dipping. Transparent, crack-free, glassy SiO₂ films of 310 ± 10 nm in thickness embedded with high mol percent of Cu–Ni alloy NPs were yielded after annealing at 750 °C in 10% H₂-90% Ar atmosphere. Nominal compositions of the films were 20 mol% (Cu–Ni)-80 mol% SiO₂. Optical spectral study of the heat-treated films showed disappearance of Cu plasmon bands due to Cu–Ni alloy formation. Grazing incidence X-ray diffraction (GIXRD) studies revealed the formation of Cu–Ni alloy (2:1, 1:1 and 1:2) NPs inside the SiO₂ film. GIXRD showed a systematic shifting of the diffraction peaks with respect to the fcc Cu–Ni alloy composition, maintaining the nominal ratios. Transmission electron microscopy (TEM) studies of the representative Cu_0.5Ni_0.5-doped film showed existence of homogeneously dispersed Cu–Ni alloy NPs of average size 6.35 nm inside the SiO₂ matrix. The energy dispersive X-ray scattering (EDX) analysis of the individual NPs using the nano-probe (scanning TEM mode) confirmed the presence of both the Cu and Ni with the desired atomic ratio.     

Ruthenium nitrosyl complexes with 1,4,7-trithiacyclononane and 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap) coligands. Electronic structure and reactivity aspects

The present article describes ruthenium nitrosyl complexes with the {RuNO}(6) and {RuNO}(7) notations in the selective molecular frameworks of [Ru(II)([9]aneS(3))(bpy)(NO(+))](3+) (4(3+)), [Ru(II)([9]aneS(3))(pap) (NO(+))](3+) (8(3+)) and [Ru(II)([9]aneS(3))(bpy)(NO˙)](2+) (4(2+)), [Ru(II)([9]aneS(3))(pap)(NO˙)](2+) (8(2+)) ([9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine), respectively. The nitrosyl complexes have been synthesized by following a stepwise synthetic procedure: {Ru(II)-Cl} → {Ru(II)-CH(3)CN} → {Ru(II)-NO(2)} → {Ru(II)-NO(+)} → {Ru(II)-NO˙}. The single-crystal X-ray structure of 4(3+) and DFT optimised structures of 4(3+), 8(3+) and 4(2+), 8(2+) establish the localised linear and bent geometries for {Ru-NO(+)} and {Ru-NO˙} complexes, respectively. The crystal structures and (1)H/(13)C NMR suggest the [333] conformation of the coordinated macrocyclic ligand ([9]aneS(3)) in the complexes. The difference in π-accepting strength of the co-ligands, bpy in 4(3+) and pap in 8(3+) (bpy < pap) has been reflected in the ν(NO) frequencies of 1945 cm(-1) (DFT: 1943 cm(-1)) and 1964 cm(-1) (DFT: 1966 cm(-1)) and E°({Ru(II)-NO(+)}/{Ru(II)-NO˙}) of 0.49 and 0.67 V versus SCE, respectively. The ν(NO) frequency of the reduced {Ru-NO˙} state in 4(2+) or 8(2+) however decreases to 1632 cm(-1) (DFT: 1637 cm(-1)) or 1634 cm(-1) (DFT: 1632 cm(-1)), respectively, with the change of the linear {Ru(II)-NO(+)} geometry in 4(3+), 8(3+) to bent {Ru(II)-NO˙} geometry in 4(2+), 8(2+). The preferential stabilisation of the eclipsed conformation of the bent NO in 4(2+) and 8(2+) has been supported by the DFT calculations. The reduced {Ru(II)-NO˙} exhibits free-radical EPR with partial metal contribution revealing the resonance formulation of {Ru(II)-NO˙}(major)?{Ru(I)-NO(+)}(minor). The electronic transitions of the complexes have been assigned based on the TD-DFT calculations on their DFT optimised structures. The estimated second-order rate constant (k, M(-1) s(-1)) of the reaction of the nucleophile, OH(-) with the electrophilic {Ru(II)-NO(+)} for the bpy derivative (4(3+)) of 1.39 × 10(-1) is half of that determined for the pap derivative (8(3+)), 2.84 × 10(-1) in CH(3)CN at 298 K. The Ru-NO bond in 4(3+) or 8(3+) undergoes facile photolytic cleavage to form the corresponding solvent species {Ru(II)-CH(3)CN}, 2(2+) or 6(2+) with widely varying rate constant values, (k(NO), s(-1)) of 1.12 × 10(-1) (t(1/2) = 6.2 s) and 7.67 × 10(-3) (t(1/2) = 90.3 s), respectively. The photo-released NO can bind to the reduced myoglobin to yield the Mb-NO adduct.