Stability constants of 2-mercaptohistamine metal complexes

Summary Stability constants of 2-mercaptohistamine (2-MH) with a number of transition metal ions were determined by a potentiometric titration method and the coordination mode of (2-MH) metal complexes were thereby characterized. With Mn^II, Fe^ll, Co^II, and Ni^II, coordination occurred through both the imidazole-nitrogen and amino groups, while with Zn^II, Cd^II, Pb^II, and Hg^II, both thiolate and amino groups, contribute to the coordination. in the 2-MH copper complex, polymer formation is suggested on the basis of visible absorption and e.p.r. spectra.     

Ionic products in ground polymer. IV. Anions in poly(vinylidene fluoride)

When poly(vinylidene fluoride) (PVDF) was ground with tetracyanoethylene (TCNE) powder in a vibration glass ball mill in vacuum in the dark at 77 K, the TCNE anion radical (TCNE-) was detected in the mixture by ESR spectroscopy. The TCNE.- is formed by the abstraction of electrons by TCNE from the anion that is produced by a heterogeneous bond scission of carbon-carbon bonds in the polymer main chain. The assignment of TCNE.- was carried out by the ESR spectral simulation on the basis of an anisotropic effective hyperfine tensor that includes a forbidden transition term. At least 85% of the bond scission of the PVDF main chain is induced by a heterogeneous process to produce ionic products. The yield of these mechanions seems to increase with the polarity of carbon-carbon bond owing to a substituent group bonded to the carbon in the polymer main chain.     

Cooperative chain relaxation in miscible polymer blends

Orientation relaxation of dissimilar chains in the molten miscible blends, poly(methyl methacrylate)/poly(vinylidene fluoride) and poly(methyl methacrylate)/poly(vinylidene fluoride-co-trifluoroethylene), were investigated by measuring (1) the change of infrared dichroic ratio with time after the uniaxial stretching of film specimens, (2) the shear stress relaxation spectrum, and (3) birefringence relaxation in shear. The dissimilar polymers showed an identical time variation of the normalized Hermans orientation function. The blend showed a relaxation spectrum with a single characteristic relaxation time τ_c, depending on the blend composition. The birefringence relaxed monotonically, remaining positive. These results suggest that the dissimilar polymers do not relax independently but cooperatively. This behavior may be induced by a constraint due to the specific interactions between the dissimilar polymers, e.g., weak hydrogen bonding. For the cooperative chain relaxation, a third power relationship was found; τ_c/τ_e vprop; (M/M_e),³ where τ_e and M_e are the relaxation time and molecular weight of entanglement strand, respectively, and M is the number average molecular weight in the blend.     

Lattice dynamics of calcium oxide

The effect of the electronic extension on the electrostatic potential was first taken into account functionally by Birman. We have applied his model to the lattice dynamics of CaO, where the degree of the electronic extension w was defined and determined with the use of the electronic charge density distribution obtained from analysis of X-ray data. Our treatment shown here not only gives a physically meaningful model including the feature of the electronic extension, but also involves essentially the same very simple process as the conventional point-charge model but with fewer adjustable parameters. Good reproduction of calculated phonon dispersion curves was obtained by taking into account the electronic extension, although the degree of the electronic extension, w, used to fit the curve was a little larger than that derived from the observed data owing to the first rough approximation for the potential energy arising from the electronic extension.     

β-Lactams via photochemical reaction of monothioimides

Photolysis of acyclic monothioimides gave β-lactams and thioamides via Type II reaction involving γ-hydrogen abstraction by thiocarbonyl group.     

A quantitative analysis of the through-space and the through-bond interactions between lone-pairs and σ-frames: S-triazine and S-tetrazine

The CNDO/2 and INDO calculations were performed on s-triazine and s-tetrazine. The s-triazine has three lone-pairs in a molecule, and these can be combined into three combinations, A, n_s and n_A. Among the three, n_s and n_A are degenerated when the whole interaction conserves its molecular point symmetry, D_3h. The s-tetrazine has four lone-pairs, which can be transformed into four combinations, SS,SA, AS and AA. The energies of these orbitals show interesting behavior. The results were subjected to an analysis from the standpoint of the through-space and through-bond interactions using the localized molecular orbitals. As a result of these analyses, the interactions were expressed by several interaction terms.     

Algorithm for in vitro Sun Protection Factor based on transmission spectrum measurement with concomitant evaluation of photostability

In the in vitro evaluation of Sun Protection Factor (SPF), the photostability of the ultraviolet (UV) filters can have a major impact, especially for high-SPF formulations, but is generally not taken into consideration. In this study, we present a UV transmission spectrum measurement system utilizing a high-sensitivity UV photomultiplier tube with concomitant evaluation of photostability. We have developed an algorithm to estimate SPF in vitro by converting the amount of UV light transmission through the sunscreen layer into cumulative relative erythema effectiveness to obtain one minimal erythema dose. Thus, the algorithm uses the same endpoint as in vivo SPF methods, but with a photomultiplier tube as the detector instead of skin. The values obtained showed an excellent correlation with in vivo SPF values, even for high-SPF sunscreens exceeding SPF 50. This method should be suitable as an in vitro SPF testing method for regulatory purposes.     

Photocontrol of spatial orientation and DNA cleavage activity of copper(II)-bound dipeptides linked by an azobenzene derivative

Copper(II) ion-bound CysGly dipeptides linked by an azobenzene derivative were photoisomerized between the trans and cis forms. The two copper(II) ion centers were positioned close to each other in the cis form, whereas they were far away from each other in the trans form. The copper complex in the cis form exhibited DNA cleavage activity, whereas the activity in the trans form was negligible. The DNA cleavage activity of the cis form is attributed to the cooperation of the closely located copper(II) centers. The present results show the photocontrol of the cooperation of metal ions for DNA cleavage.     

A novel construction of dibenzofuran-1,4-diones by oxidative cyclization of quinone-arenols

A novel oxidative cyclization of quinone-arenols 5 leading to products 6 with a dibenzofuran-1,4-dione structure, which forms the core of several natural products, has been developed and applied to the synthesis of violet-quinone (4).     

Relative stereochemistries of the ether rings and sugar moieties in durinskiol A

Durinskiol A (1) is a long carbon-chain polyol compound with a molecular weight of 2128 mu isolated from the symbiotic dinoflagellate Durinskia sp. The relative stereochemistries of ether rings and sugar moieties in 1 were established based on 2D-NMR analysis and molecular modeling studies. Conformational analysis of the 6,5,6-bis-spiroacetal ring in 1 was also examined by using ab initio methods.