Papain‐Catalyzed Chemoenzymatic Synthesis of Telechelic Polypeptides Using Bis(Leucine Ethyl Ester) Initiator

In order to construct unique polypeptide architectures, a novel telechelic‐type initiator with two leucine ethyl ester units is designed for chemoenzymatic polymerization. Glycine or alanine ethyl ester is chemoenzymatically polymerized using papain in the presence of the initiator, and the propagation occurs at each leucine ethyl ester unit to produce the telechelic polypeptide. The formation of the telechelic polypeptides is confirmed by ¹H NMR and MALDI‐TOF mass spectroscopies. It is revealed by AFM observation that long nanofibrils are formed from the telechelic polyalanine, whereas a conventional linear polyalanine with a similar degree of polymerization shows granule‐like structures. The telechelic polyglycine and polyalanine show the crystalline structures of Polyglycine II and antiparallel β‐sheet, respectively. It is demonstrated that this method to synthesize telechelic‐type polypeptides potentially opens up a pathway to construct novel hierarchical structures by self‐assembly.

     

Complexation of poly(vinyl alcohol)–congo red aqueous solutions. 3. Dynamic light scattering study

Mesoscopic structures of poly(vinyl alcohol)(SINGLEBOND)Congo red (PVA(SINGLEBOND) CR) complexes in aqueous solutions were investigated in terms of dynamic light scattering (DLS) technique. The intensity-intensity time correlation function, g⁽²⁾(t), was analyzed with an equation including a single and a stretched exponential function. Two diffusion coefficients, D_f (fast) and D_s (slow) were evaluated. D_f was converted to the apparent correlation length, ξ_app, via the mode-mode coupling hypothesis. The estimated ξ_app was insensitive to the sol(SINGLEBOND)to(SINGLEBOND)gel transition but decreased with CR concentration. This change may be related to the electrostatic screening effect. On the other hand, D_s oscillates with increasing CR concentration at a specific PVA concentration range. This explains well the reentrant sol(SINGLEBOND)gel(SINGLEBOND)sol(SINGLEBOND)gel transition behavior observed in the PVA(SINGLEBOND)CR systems. D_s seems to represent the mobility of the PVA(SINGLEBOND)CR complexes, which annihilates at the gel point. © 1996 John Wiley & Sons, Inc.     

p42MAPK-mediated phosphorylation of xEIAP/XLX in <Emphasis Type="Italic">Xenopus</Emphasis> cytostatic factor-arrested egg extracts

Background  

BIR family proteins are evolutionarily conserved anti-apoptotic molecules. One member of Xenopus BIR family proteins, xEIAP/XLX, is a weak apoptosis inhibitor and rapidly degraded in a cell-free apoptotic execution system derived from interphase egg extracts. However, unfertilized eggs are naturally arrested at the metaphase of meiosis II by the concerted activities of Mos-MEK-p42MAPK-p90Rsk kinase cascade (cytostatic factor pathway) and many mitotic kinases. Previous studies suggest that cytostatic factor-arrested egg extracts are more resistant to spontaneous apoptosis than interphase egg extracts in a p42MAPK-dependent manner. We tested whether xEIAP/XLX might be phosphorylated in cytostatic factor-arrested egg extracts, and also examined whether xEIAP/XLX could be functionally regulated by phosphorylation.     

Melting behavior of poly(oxytetramethylene)-<Emphasis Type="Italic">alt</Emphasis>-(aromatic oligoamide) block copolymers

Using temperature-modulated differential scanning calorimetry, the melting behaviour of poly(oxytetramethylene)-alt-(aromatic oligoamide) (POTM-alt-AOA) has been studied in comparison with that of polyoxytetramethylene glycohols (POTMGs). The apparent melting temperature of the block copolymers is found to be less than that of the corresponding POTMGs by approximately 30°C. The relaxation time of melting of a POTM segment has been estimated and compared with that of POTMG. The relaxation time of POTM-alt-AOA is slightly shorter than that of POTMG when the molar mass of the POTM segment is 2900; however, it is longer when the molar mass is 1400.     

Preparation and Optical Properties of Gold-Dispersed BaTiO3, PGO (Pb5Ge3O11) and PLT (Pb1-1.5xLaxTiO3) Thin Films by Sol-Gel Process

Gold-dispersed BaTiO₃, PGO and PLT thin films, which will be used for third-order nonlinear optical devices, were prepared by sol-gel process with spin-coating using HAuCl₄4H₂O, Ba(CH₃COO)₂, Ti[O(CH₂)₃CH₃]₄, Pb(CH₃COO)₂3H₂O, Ge[O-n-C₄H₉]₄, La(CH₃COO)₃1.5 H₂O as starting materials. The thin films were heat-treated in air at temperatures ranging from 400 to 800 for 1 h. The nonlinear optical property of these thin films was measured by the degenerate four-wave mixing (DFWM) method using a frequency-doubled Nd: YAG laser with 20 ps pulse duration. Third-order nonlinear susceptibility χ⁽³⁾ of gold-dispersed BaTiO₃, PGO and PLT thin films with 5 vol% of gold were 1.410⁻⁶ esu, 3.510⁻⁷ esu respectively. The large χ⁽³⁾ may be ascribed to the high dielectric constant of the films.     

Site-specific cleavage of glycated human serum albumin in the presence of iron.

Nonenzymatically glycated human serum albumin was incubated with ferric ion at 37 degrees C in 0.2 M phosphate buffer, pH 7.4, up to 30 days. In the incubation mixture, amino acids, tyrosine and phenylalanine, were detected, suggesting site specific cleavage of glycated human serum albumin.     

Synthesis of perfluorobicyclic ethers

The electrochemical fluorination of cycloalkyl-substituted acetic and propionic acids were conducted to obtain several kinds of perfluorobicyclic ethers [reaction conditions: Anodic current density: 3.5 A/dm², Volt: 5～8V, Temp: 5～6 °C] . For example, from cyclopentyl-substituted acetic acids, perfluoro(4-alkyl-2-oxabicyclo[3.3.0]octane)s (I) were formed as the cyclization products in yields of 10～19% together with the corresponding perflouroalkanoyl flourides (II) (Y=3～13%).

While, perfluorospiro-ethers were obtained from the fluorination of 3-cycloalkyl-substituted propionic acids. The characterization of these perfluorobicyclic ethers which consists of the reaction with anhydrous aluminum chloride will be reported also.     

Information Geometry and Interior-Point Algorithms in Semidefinite Programs and Symmetric Cone Programs

We develop an information geometric approach to conic programming. Information geometry is a differential geometric framework specifically tailored to deal with convexity, naturally arising in information science including statistics, machine learning and signal processing etc. First we introduce an information geometric framework of conic programming. Then we focus on semidefinite and symmetric cone programs. Recently, we demonstrated that the number of iterations of Mizuno–Todd–Ye predictor–corrector primal–dual interior-point methods is (asymptotically) expressed with an integral over the central trajectory called “the curvature integral”. The number of iterations of the algorithm is approximated surprisingly well with the integral even for fairly large linear/semidefinite programs with thousands of variables. Here we prove that “the curvature integral” admits a rigorous differential geometric expression based on information geometry. We also obtain an interesting information geometric global theorem on the central trajectory for linear programs. Together with the numerical evidence in the aforementioned work, we claim that “the number of iterations of the interior-point algorithm is expressed as a differential geometric quantity.”     

A Face of a Projective Triangulation Removed for Its Geometric Realizability

Let M be a map on a surface F ². A geometric realization of M is an embedding of F ² into a Euclidian 3-space ℝ³ with no self-intersection such that each face of M is a flat polygon. In Bonnington and Nakamoto (Discrete Comput. Geom. 40:141–157, 2008), it has been proved that every triangulation G on the projective plane has a face f such that the triangulation G−f on the M?bius band obtained from G by removing the interior of f has a geometric realization. In this paper, we shall characterize such a face f of G.