Excited-State Dynamics of [Ru(bpy)3]2+ Thin Films on Sensitized TiO2 and ZrO2

The excited state dynamics of Tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate, [Ru(bpy)₃(PF₆)₂], was investigated on the surface of bare and sensitized TiO₂ and ZrO₂ films. The organic dyes LEG4 and MKA253 were selected as sensitizers. A Stern–Volmer plot of LEG4-sensitized TiO₂ substrates with a spin-coated [Ru(bpy)₃(PF₆)₂] layer on top shows considerable quenching of the emission of the latter. Interestingly, time-resolved emission spectroscopy reveals the presence of a fast-decay time component (25±5 ns), which is absent when the anatase TiO₂ semiconductor is replaced by ZrO₂. It should be specified that the positive redox potential of the ruthenium complex prevents electron transfer from the [Ru(bpy)₃(PF₆)₂] ground state into the oxidized sensitizer. Therefore, we speculate that the fast-decay time component observed stems from excited-state electron transfer from [Ru(bpy)₃(PF₆)₂] to the oxidized sensitizer. Solid-state dye sensitized solar cells (ssDSSCs) employing MKA253 and LEG4 dyes, with [Ru(bpy)₃(PF₆)₂] as a hole-transporting material (HTM), exhibit 1.2 % and 1.1 % power conversion efficiency, respectively. This result illustrates the possibility of the hypothesized excited-state electron transfer.     

Ultrasensitive separation of methylprednisolone acetate using a photoresponsive molecularly imprinted polymer incorporated polyester dendrimer based on magnetic nanoparticles

We developed an approach for the use of polyester dendrimer during the imprinting process to raise the number of recognized sites in the polymer matrix and improve its identification ability. Photoresponsive molecularly imprinted polymers were synthesized on modified magnetic nanoparticles involving polyester dendrimer which uses the reactivity between allyl glycidyl ether and acrylic acid for the high‐yielding assembly by surface polymerization. The photoresponsive molecularly imprinted polymers were constructed using methylprednisoloneacetate as the template, water‐soluble azobenzene involving 5‐[(4, 3‐(methacryloyloxy) phenyl) diazenyl] dihydroxy aniline as the novel functional monomer, and ethylene glycol dimethacrylate as the cross‐linker. Through the evaluation of a series of features of spectroscopic and nano‐structural, this sorbent showed excellent selective adsorption, recognition for the template, and provided a highly selective and sensitive strategy for determining the methylprednisoloneacetate in real and pharmaceutical samples. In addition, this sorbent according to good photo‐responsive features and specific affinity to methylprednisoloneacetate with high recognition ability, represented higher binding capacity, a more extensive specific area, and faster mass transfer rate than its corresponding surface molecularly imprinted polymer.     

Modification of WS2 nanosheets with beta-cyclodextrone and N-isopropylacrylamide polymers for tamoxifen adsorption and investigation of in vitro drug release

In this research, tungsten disulfide (WS₂) nanosheets were modified with beta-cyclodextrone (βCD) N-isopropylacrylamide polymers (NIPAAP) for adsorption of tamoxifen (TAM) drug. The synthesized WS₂/βCD/NIPAAP samples were characterized by field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) analyses. The adsorption experiments of TAM on WS₂/βCD/NIPAAP were performed as a function of pH, reaction contact time, temperature and drug concentration. The adsorption kinetic data were well fitted to the pseudo-second-order model. Also, the equilibrium data were well described by Langmuir isotherm model. The maximum adsorption capacity of WS₂/βCD/NIPAAP for TAM drug was found to be 62.0 mg/g. The results of regeneration tests showed that the synthesized WS₂/βCD/NIPAAP adsorbent can be easily reused after 6 cycles of adsorption–desorption. Furthermore, TAM drug release was investigated in a simulated system with pH 7.4 at different temperatures. The results showed that the release of TAM drug from WS₂/βCD/NIPAAP carrier at 50 °C and 37 °C was greater than TAM release at 25 °C. Also, the experimental data of drug release were studied by Higuchi, Ritger-Peppas, zero-order and first-order models. The release data were well fitted to the zero-order model indicating a case II transport. The results showed a high stability for TAM drug.

     

Some Lower Bounds in the B. and M. Shapiro Conjecture for Flag Varieties

The B. and M. Shapiro conjecture stated that all solutions of the Schubert Calculus problems associated with real points on the rational normal curve should be real. For Grassmannians, it was proved by Mukhin, Tarasov, and Varchenko. For flag varieties, Sottile found a counterexample and suggested that all solutions should be real under certain monotonicity conditions. In this paper, we compute lower bounds on the number of real solutions for some special cases of the B. and M. Shapiro conjecture for flag varieties, when Sottile’s monotonicity conditions are not satisfied.     

Dithienylethene-Based Single Molecular Photothermal Linear Actuator

By employing a mechanically controllable break junction technique, we have realized an ideal single molecular linear actuator based on dithienylethene (DTE) based molecular architecture, which undergoes reversible photothermal isomerization when subjected to UV irradiation under ambient conditions. As a result, open form (compressed, UV OFF) and closed form (elongated, UV ON) of dithienylethene-based molecular junctions are achieved. Interestingly, the mechanical actuation is achieved without changing the conductance of the molecular junction around the Fermi level over several cycles, which is an essential property required for an ideal single molecular actuator. Our study demonstrates a unique example of achieving a perfect balance between tunneling width and barrier height change upon photothermal isomerization, resulting in no change in conductance but a change in the molecular length, which results in mechanical actuation at the single molecular level.