D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.     

On the Whitham Equations for the Defocusing Nonlinear Schrodinger Equation with Step Initial Data

The behavior of solutions of the finite-genus Whitham equations for the weak dispersion limit of the defocusing nonlinear Schrodinger equation is investigated analytically and numerically for piecewise-constant initial data. In particular, the dynamics of constant-amplitude initial conditions with one or more frequency jumps (i.e., piecewise linear phase) are considered. It is shown analytically and numerically that, for finite times, regions of arbitrarily high genus can be produced; asymptotically with time, however, the solution can be divided into expanding regions which are either of genus-zero, genus-one, or genus-two type, their precise arrangement depending on the specifics of the initial datum given. This behavior should be compared to that of the Korteweg-de Vries equation, where the solution is divided into regions which are either genus-zero or genus-one asymptotically. Finally, the potential application of these results to the generation of short optical pulses is discussed: The method proposed takes advantage of nonlinear compression via appropriate frequency modulation, and allows control of both the pulse amplitude and its width, as well as the distance along the fiber at which the pulse is produced     

Precise synthesis of porphyrin array scaffolding polyisocyanides

Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006     

Hasse-Witt matrices of Fermat curves

Let m be an integer with m3. Let K and K be perfect fields of characteristic p and p such that (p,m)=1 and (p,m)=1, respectively. Moreover let A and A be algebraic function fields over K and K defined by x^m+y^m=a(0, ak) and x^m+y^m=a(a0 ak), respectively. Put g=(m–1)(m–2)/2. Denote by M(K,p,a) and M(K,p,a) the Hasse-Witt matrices of A and A with respect to the canonical bases of holomorphic differentials. Then we show that if p+p0(mod.m) then rank M(K,p,a)+rank M(K,p,a)=g and if pp1 (mod.m) then rank M(K,p,a)=rank M(K,p,a).     

Structures of americanol A and isoamericanol A having a neurotrophic property from the seeds of Phytolacca americana.

The structures of new neo-lignans, isoamericanol A (1) and americanol A (2) isolated from the seeds of Phytolacca americana have been elucidated on the basis of spectroscopic data and then confirmed by chemical correlation with the previously known isoamericanin A (3) and americanin A (4). Isoamericanol A, americanol A, and americanin A have been found to enhance choline acetyltransferase activity at 10(-5) M in a cultured neuronal cell system derived from fetal rat hemisphere.     

Regional cerebral blood flow measurement in brain tumors

The regional cerebral blood flow (CBF) was determined on seventeen patients with brain tumors. Ring type single photon emission CT (SPECT) was used following intravenous injection of 133Xe. Case materials included eleven meningiomas and six malignant gliomas. Evaluation was performed with emphasis on the following points; Correlation of the flow data within tumors to the angiographic tumor stains, Influence of tumors on the cerebral blood flow of the normal brain tissue, Correlation between degree of peripheral edema and the flow data of the affected hemispheres. There was significant correlation between flow data within tumors and angiographic tumor stains in meningiomas. Influence of tumors on cerebral blood flow of the normal tissue was greater in meningiomas than in gliomas. There was negative correlation between the degree of peripheral edema and the flow data of the affected hemisphere. It has been concluded that the measurement of CBF in brain tumors is a valuable method in evaluation of brain tumors.