Mechanistic understanding of the translational movements in molecular switches is essential for designing machine-like prototypes capable of following set pathways of motion. To this end, we demonstrated that increasing the station-to-station distance will speed up the linear movements forward and slow down the movements backward in a homologous series of bistable rotaxanes. Four redox-active rotaxanes, which drove a cyclobis(paraquat-p-phenylene) (CBPQT(4+)) mobile ring between a tetrathiafulvalene (TTF) station and an oxyphenylene station, were synthesized with only variations to the lengths of the glycol linker connecting the two stations (n = 5, 8, 11, and 23 atoms). We undertook the first mechanistic study of the full cycle of motion in this class of molecular switch using cyclic voltammetry. The kinetics parameters (k, ΔG(‡)) of switching were determined at different temperatures to provide activation enthalpies (ΔH(‡)) and entropies (ΔS(‡)). Longer glycol linkers led to modest increases in the forward escape (t(1/2) = 60 to <7 ms). The rate-limiting step involves movement of the tetracationic CBPQT(4+) ring away from the singly oxidized TTF(+) unit by overcoming one of the thiomethyl (SMe) speed bumps before proceeding on to the secondary oxyphenylene station. Upon reduction, however, the return translational movement of the CBPQT(4+) ring from the oxyphenylene station back to the neutral TTF station was slowed considerably by the longer linkers (t(1/2) = 1.4 to >69 s); though not because of a diffusive walk. The reduced rate of motion backward depended on folded structures that were only present with longer linkers.
The development of Ru(II) functionalized gold nanoparticles 1–3·AuNP is described. These systems were found to be mono-disperse with a hydrodynamic radius of ca. 15 nm in water but gave rise to the formation of higher order structures in buffered solution. The interaction of 1–3·AuNP with DNA was also studied by spectroscopic and microscopic methods and suggested the formation of large self-assembly structures in solution. The uptake of 1–3·AuNP by cancer cells was studied using both confocal fluorescence as well as transmission electron microscopy (TEM), with the aim of investigating their potential as tools for cellular biology. These systems displaying a non-toxic profile with favourable photophysical properties may have application across various biological fields including diagnostics and therapeutics.
The synthesis, photophysics and biological investigation of fluorescent 4-amino-1,8-naphthalimide Tröger's bases (TB-1-TB-3) and a new Tröger's base p-cymene-Ru(ii)-curcumin organometallic conjugate (TB-Ru-Cur) are described; these compounds showed fast cellular uptake and displayed good luminescence and cytotoxicity against cervical cancer cells.
A unique V-shaped "chiral" supramolecular scaffold, N-(4-pyridyl)-4-amino-1,8-naphthalimide Troger's base (TBNap), was synthesized in good yield from a precursor N-(4-pyridyl)-4-amino-1,8-naphthalimide (Nap). TBNap was characterized using different spectroscopic methods and the molecular structure was elucidated by diffraction analysis. A new pcymene-Ru(II)-curcumin conjugate (TB-Ru-Cur) was designed by reacting TBNap dipyridyl donor and ruthenium-curcuminato acceptor [RuCur = (p-cymene)Ru-(curcuminato)Cl] in the presence of silver triflate. TB-Ru-Cur was isolated in quantitative yield and characterized using Fourier transform infrared (FT-IR), NMR ( 1 H, 13 C, and 19 F), and electrospray ionization mass spectrometry (ESI-MS), and the molecular structure has been predicted using a computational study. Both TBNap and TB-Ru-Cur exhibited intramolecular charge transfer (ICT)-based fluorescence emission. Furthermore, the anticancer properties of TBNap, Ru-Cur, and TB-Ru-Cur were assessed in different cancer cell lines. Gratifyingly, the conjugate TB-Ru-Cur displayed fast-cellular internalization and good cytotoxicity against HeLa, HCT-116, and HepG2 cancer cells and the estimated IC 50 value was much lower than that of the precursors (TBNap and Ru-Cur) and the well-known chemotherapeutic drug cisplatin.
A flexible ditopic ligand 1 containing two N,N,O-tridentate (1,2,3-triazol-4-yl)-picolinamide chelating pockets is reported and the formation of multimetallic architectures is explored in the solid and the solution phase. The self-assembled Zn complex [Zn(1)](ClO) exhibited a folded [2 × 2] square grid supramolecular architecture that selectively assembled in MeCN solution as shown using various spectroscopic techniques. The closely related Fe complex shows equivalent behaviour in the solid state, while a discrete dinuclear species [Cu(NO)1]·5MeCN was the sole product observed in the solid state from the reaction between 1 and Cu under similar conditions.
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