Vicinal Tetraamines of Defined Geometry: Potential Scaffolds for Assembly

The syntheses of tetraamines 10 (Scheme 3) and 17 (Scheme 4), which might be useful as rigid organizing scaffolds in dynamic or standard combinatorial chemistry, are described. The Diels‐Alder reaction of the electron‐rich dienophile 1,3‐diacetyl‐2,3‐dihydro‐1H‐imidazol‐2‐one ( 5 ) with benzo[c]thiophene or 2H‐pyran‐2‐one is the key step in their preparation. The intermediate fused cyclic diureas 9 and 16 are dimethylglycoluril analogues, and their crystal structures are examined. Diurea 9 (Fig. 2) crystallizes as a hydrate and forms undulating chains through a network of H‐bonds. These chains are interconnected through H‐bonds to the H₂O molecules. H₂O Molecules are not incorporated in the crystal of `bis‐urea' 16 (Fig. 3), the molecules of which associate through an extended three‐dimensional H‐bonding network.     

Paclitaxel‐Loaded Stabilizer‐Free Poly(D,L‐lactide‐co‐glycolide) Nanoparticles Conjugated with Quantum Dots for Reversion of Anti‐Cancer Drug Resistance and Cancer Cellular Imaging

We prepared the PLGA‐loaded anti‐cancer drug and coated it with quantum dots to make it a dual‐function nanoparticles, and analyzed its potential use in cellular imaging and curing cancers. Two cancer cell lines, paclitaxel‐sensitive KB and paclitaxel‐resistant KB paclitaxel‐50 cervical carcinoma cells, were the relativistic models for analysis of the cytotoxicity of free paclitaxel and paclitaxel‐loaded PLGA conjugated with quantum‐dot nanoparticles. The paclitaxel‐loaded PLGA conjugated with quantum dots nanoparticles were significantly more cytotoxic than the free paclitaxel drug in paclitaxel‐resistant KB paclitaxel‐50 cells. This might have been because the cancer cells developed multi‐drug resistance (MDR), which hampered the action of free paclitaxel by pumping its molecules to extracellular areas. Addition of verapamil, a P‐glycoprotein inhibitor, reversed the MDR mechanism and significantly reduced KB paclitaxel‐50 cell viability. As a result, KB paclitaxel‐50 was highly associated with MDR on the cell membrane. The cytotoxicity results indicated that PLGA nanoparticles served as drug carriers and protected the drugs from MDR‐accelerated efflux. Combined quantum dots with PLGA nanoparticles allowed additional functionality for cellular imaging.     

磁瓶式光电子能谱和速度成像光电子能谱对APS-(A=C14H10,蒽)的研究:电子结构,APS·的自旋轨道耦合和APS-的自旋偶极态

Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS^-(A=C₁₄H₁₀ or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit (SO) splitting of the APS^· radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA=(2.62±0.05) eV and SO splitting=(43±7) meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31++G(d,p) calculations indicate APS^· has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.     

μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge

Diuranium μ-η(6),η(6)-arene complexes supported by ketimide ligands were synthesized and characterized. Disodium or dipotassium salts of the formula M(2)(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (M = Na or K, Mes = 2,4,6-C(6)H(2)Me(3)) and monopotassium salts of the formula K(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (arene = naphthalene, biphenyl, trans-stilbene, or p-terphenyl) were both observed. Two different salts of the monoanionic, toluene-bridged complexes are also described. Density functional theory calculations have been employed to illuminate the electronic structure of the μ-η(6),η(6)-arene diuranium complexes and to facilitate the comparison with related transition-metal systems, in particular (μ-η(6),η(6)-C(6)H(6))[VCp](2). It was found that the μ-η(6),η(6)-arene diuranium complexes were isolobal with (μ-η(6),η(6)-C(6)H(6))[VCp](2) and that the principal arene-binding interaction was a pair of δ bonds (total of 4e) involving both metals and the arene lowest unoccupied molecular orbital. Reactivity studies have been carried out with the mono- and dianionic μ-η(6),η(6)-arene diuranium complexes, revealing contrasting modes of redox chemistry as a function of the system's state of charge.     

Brillouin and raman scattering studies of the melting transition in salol

Brillouin and Raman scattering studies of salol from room temperature to within 5 mK of the melting transition at T_m = 40.97°C are reported. Changes in the Brillouin shifts and linewidths were accurately determined by nonlinear least-squares fitting and deconvolution. A marked increase in the deconvoluted Brillouin linewidth (~400%) and a gradual softening (~20%) of the transverse acoustic modes were observed very close to T_m. The increase of the Brillouin linewidths was analyzed by a simple dislocation model assuming the hypersonic attenuation to be proportional to the concentration of thermally generated defects near T_m. The defect formation energy E_D(T) was computed from the temperature-dependent linewidth data, and was found to decrease significantly (~60%) near T_m, suggesting a cooperative effect producing a catastrophic growth of defects which brings about melting by destroying the long range order of the crystal. The conclusion that melting is mediated by a sudden growth of defect concentration near T_m was further strengthened by Raman scattering experiments in which 13 new Raman modes appeared close to T_m. These new modes are believed to be defect activated through breaking of the local symmetry of the crystal. A slight softening of the Raman modes (~5%) was observed close to the melting point.     

Comparing Classes of Finite Structures

We compare classes of structures using the notion of a computable embedding, which is a partial order on the classes of structures. Our attention is mainly, but not exclusively, focused on classes of finite structures. Also, a number of problems are formulated.