Supramolecular Host‐Inhibited Excited‐State Proton Transfer and Fluorescence Switching of the Anti‐Cancer Drug,Topotecan

The effect of cucurbit[7]uril (CB[7]) nano‐caging on the photophysical properties, particularly excited‐state proton transfer (ESPT) reaction, of an eminent anti‐cancer drug, topotecan (TPT), is demonstrated through steady‐state and time‐resolved fluorescence measurements. TPT in water (pH 6) exists exclusively as the cationic form (C) in the ground state. However, the drug emission mainly comes from the excited‐state zwitterionic form (Z*) of TPT, and is attributed to water‐assisted ESPT between the 10‐hydroxyl group and water, which leads to the transformation of C* to Z* of TPT. In the presence of CB[7], it is found that selective encapsulation of the C form of TPT results in the formation of a 1:1 inclusion complex (CB[7]:TPT), and the ESPT process is inhibited by this encapsulation process. As a result, C* becomes the dominant emitting species in the presence of CB[7] rather than Z*, and fluorescence switching takes place from green to blue. Time‐resolved studies also support the existence of CB[7]‐encapsulated cationic species as the major emitting species in the presence of the macrocyclic host. Semi‐empirical quantum chemical calculations are employed to gain insight into the molecular picture of orientation of TPT in the inclusion complex. It is clearly seen from the optimised structure of 1:1 CB[7]:TPT inclusion complex that both 10‐hydroxyl and 9‐dimethylaminomethylene groups of TPT lie partly inside the cavity, and thereby inhibit the excited‐state transformation of C* to Z* by the ESPT process. Finally, controlled release of the drug is achieved by means of fluorescence switching by introducing NaCl, which is rich in cells, as an external stimulus.     

Spectroscopic and Theoretical Investigations on Supramolecular Interaction of a Newly Designed Monoporphyrin with Fullerenes and Functionalized Fullerenes in Solution

The present paper reports the results of a photophysical investigation of a designed monoporphyrin (1) and its supramolecular complexes with C₆₀, C₇₀ and derivatized fullerenes, namely tert-butyl-(1,2-methanofullerene)-61-carboxylate (2) and [6,6]-phenyl C₇₁ butyric acid methyl ester (3) in toluene. UV–vis studies reveal appreciable ground state interaction between the fullerenes and compound 1. Steady state fluorescence studies show quenching of fluorescence of 1 in the presence of fullerenes. The binding constants of the C₆₀/1, C₇₀/1, 2/1 and 3/1 complexes are estimated to be 300, 20770, 1150 and 13170 dm³⋅mol⁻¹, respectively. Molecular mechanics calculations in vacuo evoke the stereoscopic structures of the fullerene/1 complexes and allow interpretation of the stability difference among various fullerene complexes of 1 in terms of their enthalpies of formation.     

Near-ground tornado-like vortex structure resolved by particle image velocimetry (PIV)

The near-ground flow structure of tornadoes is of utmost interest because it determines how and to what extent civil structures could get damaged in tornado events. We simulated tornado-like vortex flow at the swirl ratios of S = 0.03–0.3 (vane angle θ_v = 15°–60°), using a laboratory tornado simulator and investigated the near-ground-vortex structure by particle imaging velocimetry. Complicated near-ground flow was measured in two orthogonal views: horizontal planes at various elevations (z = 11, 26 and 53 mm above the ground) and the meridian plane. We observed two distinct vortex structures: a single-celled vortex at the lowest swirl ratio (S = 0.03, θ_v = 15°) and multiple suction vortices rotating around the primary vortex (two-celled vortex) at higher swirl ratios (S = 0.1–0.3, θ_v = 30°–60°). We quantified the effects of vortex wandering on the mean flow and found that vortex wandering was important and should be taken into account in the low swirl ratio case. The tangential velocity, as the dominant velocity component, has the peak value about three times that of the maximum radial velocity regardless of the swirl ratio. The maximum velocity variance is about twice at the high swirl ratio (θ_v = 45°) that at the low swirl ratio (θ_v = 15°), which is contributed significantly by the multiple small-scale secondary vortices. Here, the results show that not only the intensified mean flow but greatly enhanced turbulence occurs near the surface in the tornado-like vortex flow. The intensified mean flow and enhanced turbulence at the ground level, correlated with the ground-vortex interaction, may cause dramatic damage of the civil structures in tornadoes. This work provides detailed characterization of the tornado-like vortex structure, which has not been fully revealed in previous field studies and laboratory simulations. It would be helpful in improving the understanding of the interaction between the tornado-like vortex structure and the ground surface, ultimately leading to better predictions of tornado-induced wind loads on civil structures.     

Implementation of tristate logic based all optical flip-flop with nonlinear material

The advantages of multivalued logic in optical parallel computation need no introduction. There are lots of proposals, already reported, where tristate, quarternary state logic operations can be performed with optics. Here we report a new approach to implement tristate logic based all optical flip-flop using optical nonlinear material. The concept and the principle of operation of this type of flip-flop are different from that of the conventional binary one.     

Isomerization and fluorescence depolarization of merocyanine 540 in polyacrylic acid. Effect of p H

Dynamics of isomerization and fluorescence depolarization of merocyanine 540 (MC540) in an aqueous solution of polyacrylic acid (PAA) have been studied using picosecond time resolved fluorescence spectroscopy. It is observed that the dynamics of isomerization and depolarization are sensitive enough to monitor the uncoiling of PAA at high pH (> 6). At low pH (< 3), when the polymer remains in a hypercoiled form, polymer bound MC540 experiences very high microscopic friction and, hence, the isomerization and depolarization processes are very slow. At high pH (> 6) a polyanion is formed and the polymer assumes an extended configuration due to electrostatic repulsion. At high pH (> 6), the anionic probe MC540 is expelled from the polyanion to bulk water and the dynamics of isomerization and fluorescence depolarization become faster by 12 and 5 times respectively, compared to those at low pH.     

Electrophoresis of soft particles with charged rigid core coated with pH-regulated polyelectrolyte layer

We present a theoretical study on the electrophoresis of a soft particle with a dielectric charged rigid core grafted with a charge-regulated polyelectrolyte layer. The polyelectrolyte layer possesses either an acidic or a basic functional group and the charge dissociation depends on the local pH and ionic concentration of the electrolyte. The dielectric rigid core is considered to possess a uniform volumetric charge density. The electric potential distribution is determined by computing the Poisson-Boltzmann equation outside the core coupled with a Poisson equation inside the impermeable core along with suitable matching conditions at the core-shell interface. The computed electric field is used to determine the mobility of the particle through an existing analytic expression based on the Debye-Huckel approximation. Our results are found to be in good agreement with the existing solutions for the limiting cases. The influence of the core charge density, ionic concentration, and pH of the electrolyte on the particle mobility is studied for different choice of hydrodynamic penetration length of the polyelectrolyte and dissociation constant of the functional group. The critical value of the pH required to achieve zero mobility is estimated. We find that in a monovalent electrolyte solution, the soft particle with a net negative (positive) charge can have positive (negative) mobility.     

A new series of three-dimensional metal-organic framework, [M2(H2O)][C5N1H3(COO)2]3.2H2O, M = La, Pr, and Nd: synthesis, structure, and properties

A new series of lanthanide pyridine dicarboxylates of the general formula, [M2(H2O)][C5N1H3(COO)2]3.2H2O, M = La (1), Pr (2), and Nd (3), has been prepared by the reaction of trivalent lanthanide salts and pyridine dicarboxylic acids employing a mild condition hydrothermal reaction. The structures are built up from MO8N and MO7N2 (M = lanthanide) polyhedra connected to the dicarboxylate anions forming the three-dimensional structure with one-dimensional channels. A striking feature of this structure is the presence of an unusual Z-shaped tetramer of the formula M4O24N6. Extraframework water molecules, located within the open channels, are reversibly adsorbed. Detailed in situ and ex situ investigations using FTIR and PXRD studies clearly show that the removal of the water molecules is reversible and accompanied by changes in the size of the channel. Partial substitution at the La sites by Eu gives rise to characteristic red-pink luminescence, indicating a ligand-sensitized metal-centered emission.     

Torus Equivariant Spectral Triples for Odd-Dimensional Quantum Spheres Coming from <Emphasis Type="Italic">C</Emphasis><Superscript>*</Superscript>-Extensions

The torus group (S ¹)^ℓ+1 has a canonical action on the odd-dimensional sphere S _q ^2ℓ+1. We take the natural Hilbert space representation where this action is implemented and characterize all odd spectral triples acting on that space and equivariant with respect to that action. This characterization gives a construction of an optimum family of equivariant spectral triples having nontrivial K-homology class thus generalizing our earlier results for SU _q (2). We also relate the triple we construct with the C ^*-extension      

Single-crystal to single-crystal phase transitions of bis(N-phenylisonicotinamide)silver(I) nitrate reveal cooperativity properties in porous molecular materials

Two single-crystal to single-crystal phase transitions in trans-[Ag(NPI)(2)](NO(3)).2CH(3)OH (), (NPI = N-phenylisonicotinamide) were characterized with X-ray crystallography; the first transition is reversible and arises from a desolvation transition induced by vacuum and generated ; the second transition was induced by heat at 140 degrees C and generated .     

Binding and templation of nanoparticle receptors to peptide alpha-helices through surface recognition

Nanoparticles featuring highly flexible sidechains template to peptides, demonstrating substantial pre-organization of the particle monolayer.