Femtosecond/picosecond time-resolved fluorescence study of hydrophilic polymer fine particles

Femtosecond/picosecond time-resolved fluorescence study of hydrophilic polymer fine particles (polyacrylamide, PAAm) was reported. Ultrafast fluorescence dynamics of polymer/water solution was monitored using a fluorescent probe molecule (C153). In the femtosecond time-resolved fluorescence measurement at 480 nm, slowly decay components having lifetimes of tau(1) approximately 53 ps and tau(2) approximately 5 ns were observed in addition to rapid fluorescence decay. Picosecond time-resolved fluorescence spectra of C153/PAAm/H2O solution were also measured. In the time-resolved fluorescence spectra of C153/PAAm/H2O, a peak shift from 490 to 515 nm was measured, which can be assigned to the solvation dynamics of polymer fine particles. The fluorescence peak shift was related to the solvation response function and two time constants were determined (tau(3) approximately 50 ps and tau(4) approximately 467 ps). Therefore, the tau(1) component observed in the femtosecond time-resolved fluorescence measurement was assigned to the solvation dynamics that was observed only in the presence of polymer fine particles. Rotational diffusion measurements were also carried out on the basis of the picosecond time-resolved fluorescence spectra. In the C153/PAAm/H2O solution, anisotropy decay having two different time constants was also derived (tau(6) approximately 76 ps and tau(7) approximately 676 ps), indicating the presence of two different microscopic molecular environments around the polymer surface. Using the Stokes-Einstein-Debye (SED) equation, microscopic viscosity around the polymer surface was evaluated. For the area that gave a rotational diffusion time of tau(6) approximately 76 ps, the calculated viscosity is approximately 1.1 cP and for tau(7) approximately 676 ps, it is approximately 10 cP. The calculated viscosity values clearly revealed that there are two different molecular environments around the polyacrylamide fine particles.     

A path-probability representation for wavefunctions

A mathematical representation of the quantum mechanical wavefunction in terms of path-probability is presented. It provides an interesting reformulation of Feynman's path-integrals. The whole results are natural consequences of stochastic calculus of variations.     

Residual‐density mapping and site‐selective determination of anomalous scattering factors to examine the origin of the Fe K pre‐edge peak of magnetite

The electron‐density distribution and the contribution to anomalous scattering factors for Fe ions in magnetite have been analyzed by X‐ray resonant scattering at the pre‐edge of Fe K absorption. Synchrotron X‐ray experiments were carried out using a conventional four‐circle diffractometer in the right‐handed circular polarization. Difference‐Fourier synthesis was applied with a difference in structure factors measured on and off the pre‐edge (E_on = 7.1082 keV, E_off = 7.1051 keV). Electron‐density peaks due to X‐ray resonant scattering were clearly observed for both A and B sites. The real part of the anomalous scattering factor f′ has been determined site‐independently, based on the crystal‐structure refinements, to minimize the squared residuals at the Fe K pre‐edge. The f′ values obtained at E_on and E_off are ?7.063 and ?6.682 for the A site and ?6.971 and ?6.709 for the B site, which are significantly smaller than the values of ?6.206 and ?5.844, respectively, estimated from the Kramers–Kronig transform. The f′ values at E_on are reasonably smaller than those at E_off. Our results using a symmetry‐based consideration suggest that the origin of the pre‐edge peak is Fe ions occupying both A and B sites, where p–d mixing is needed with hybridized electrons of Fe in both sites overlapping the neighbouring O atoms.     

Antitumor enediyne chromoprotein C-1027: mechanistic investigation of the chromophore-mediated self-decomposition pathway

C-1027 is an extremely potent antitumor agent that causes double-stranded DNA cleavages. It is a unique small molecule-protein complex composed of a highly reactive enediyne chromophore, which upon binding reacts with its target molecule DNA through radical-mediated hydrogen abstraction and an apoprotein that encapsulates the chromophore serving as its carrier to reach DNA. Although C-1027 has favorable properties as an effective drug delivery system, it slowly self-decomposes due to the reactivity of the chromophore toward the apoprotein. Understanding how the C-1027 destroys itself may enable design of its analogues that overcome this limitation. In this paper, mechanistic insights into the self-reactivity of C-1027 that facilitates its own decomposition are described. We provide evidence that the formation of the Gly96 radical, which promotes the oxidative protein scission and the subsequent chromophore release, is the major pathway for the self-decomposition of C-1027. On the basis of the newly isolated products of the self-decomposition, we propose that the apoprotein effectively protects two different structural elements of the chromophore that are essential for its biological activity: the nine-membered enediyne moiety (necessary for DNA cleavage) and the benzoxazine moiety (necessary for DNA intercalation). Using an engineered apoprotein analogue kinetically more stable toward the chromophore radical, we show that enhanced overall properties can be achieved for the natural C-1027 with respect to stability and antitumor activities. The results present the first example of a rationally designed C-1027 analogue reported to display superior in vitro antitumor activity to the natural C-1027. Our findings may have implications for design of proteins that can stably encapsulate highly reactive small molecules.     

Modified Yamaguchi Reagent: Convenient and Efficient Esterification

A convenient and efficient esterification method that used a modified Yamaguchi reagent (2,4,6-trichlorobenzoyl chloride–4-dimethylaminopyridine) and avoided use not only of intractable acid chloride but also of acid anhydrides was proposed. The reaction mechanism was described by Fourier transform infrared spectroscopy and supported by a density functional theory calculation.     

Effects of dipole interaction and solvation on the CO stretching band of N,N-dimethylacetamide in nonpolar solutions: Infrared, isotropic and anisotropic Raman measurements

The concentration dependence of the CO stretching (ν_CO) band of N,N-dimethylacetamide (NdMA) in cyclohexane, n-hexane, and CCl₄ has been investigated by infrared (IR) and polarized Raman spectroscopy. For the neat liquid of NdMA, the noncoincidence of the aniso- and isotropic Raman wavenumbers is evident. In the 0.47 M cyclohexane solution of NdMA, the noncoincidence effect almost disappears and the ν_CO envelopes in both the Raman and IR spectra are asymmetric to the low-wavenumber side. When the concentration of NdMA decreases from 0.33 to 0.023 M, the peak of these bands slightly shifts to a higher wavenumber and the band shape becomes symmetric. The shape of the ν_CO envelope does not show any significant change below 0.023 M. These results suggest that the asymmetric shape of the ν_CO band observed for the 0.33 M cyclohexane solution is associated with the intermolecular interaction among NdMA molecules, which vanishes at around 0.02 M. Spectral changes for the CCl₄ solution of NdMA show a similar tendency. However, the shape and peak wavenumber of the ν_CO band observed in a highly diluted CCl₄ solution (≤0.023 M) indicate that the solvation effect of CCl₄ is more complicated than those of cyclohexane and n-hexane. The analyses of the ν_CO band, which is sensitive to the intermolecular interaction between solutes and between solute and solvent for NdMA dissolved in nonpolar solvents, would serve to clarify the electronic property of the molecule in a solution.     

Crystal structure of Diels-Alder cycloadduct formed from 1-(1,2,3-1H-benzotriazol-1-yl)-2-(4-methylphenyl)-2H-isoindole and dimethyl acetylenedicarboxylate.

The structure of the Diels-Alder cycloadduct formed from 2-(1,2,3-1H-benzotriazol-1-yl)-2-(p-tolyl)-2H-isoindole and dimethyl acetylenedicarboxylate was proved as 11-aza-1-(1,2,3-1H-benzotriazol-1-yl)-11-(4-methylphenyl)-tricyclo-[5.2.1.0(2.7)]undeca-2,4,6.9-tetraene-9,10-dioic acid dimethyl ester. The benzotriazole moiety was located as its 1-yl form, analogous to previous reports. The benzotriazole and the benzene (of tricyclo framework) planes were twisted with an angle of 115.83 degrees. Intramolecular close contacts between benzotriazole and ester are characteristic [N(3)...C(26), 2.754(3)A; N(3)...H(22), 3.26(4)A]. The shortest contact of N(3)...H(22) accounting for the rotation of the methyl group is estimated to be 3.10 A, which might be reasonable as C-H...N-type hydrogen bonding.     

Hydration of the organized molecular assembly of ionic surfactants as studied by vapor pressure and x-ray diffraction

Equilibrium vapor pressure of water was measured for ionic surfactant-water binary systems as a function of water content over the temperature range 5–11°C. The measurement of x-ray powder diffraction has also been performed to characterize the microscopic structures of these two-component systems. Examined surfactants were the homologs of sodium alkyl sulfate and alkyltrimethylammonium bromide. It was found that dodecyl and decyl sulfate formed solid di-and trihydrate respectively, while octyl sulfate and the cationic surfactants formed lyotropic liquid crystal instead. The x-ray long spacing of the liquid crystals scarcely varied with water content.Enthalpy of vaporization was calculated for both solid hydrates and lyotropic liquid crystals.     

In-situ observation of graphene growth on Ni(111)

Graphene growth of mono-, bi- and tri-layers on Ni(111) through surface segregation was observed in situ by low energy electron microscopy. The carbon segregation was controlled by adjusting substrate temperature from 1200 K to 1050 K. After the completion of the first layer at 1125 K, the second layer grew at the interface between the first-layer and the substrate at 1050 K. The third layer also started to grow at the same temperature, 1050 K. All the layers exhibited a 1 × 1 atomic structure. The edges of the first-layer islands were straight lines, reflecting the hexagonal atomic structure. On the other hand, the shapes of the second-layer islands were dendritic. The edges of the third-layer islands were again straight lines similar to those of the first-layer islands. The phenomena presumably originate from the changes of interfacial-bond strength of the graphene to Ni substrate depending on the graphene thickness. No nucleation site of graphene layers was directly observed. All the layers expanded out of the field of view and covered the surface. The number of nucleation sites is extremely small on Ni(111) surface. This finding might open the way to grow the high quality, single-domain graphene crystals.