Chemical Synthesis of O‐Glycosylated Human Interleukin‐2 by the Reverse Polarity Protection Strategy

The chemical synthesis of human interleukin‐2 (IL‐2) , having a core 1 sugar, by a ligation method is reported. Although IL‐2 is a globular glycoprotein, its C‐terminal region, in particular (99‐133), is extremely insoluble when synthesized by solid‐phase method. To overcome this problem, the side‐chain carboxylic acid of the Glu residues was protected by a picolyl ester, thus reversing its polarity from negative to positive. This reverse polarity protection significantly increased the isoelectric point of the peptide segment and made it positive under acidic conditions and facilitated the purification. An efficient method to prepare the prolyl peptide thioester required for the synthesis of the (28‐65) segment was also developed. These efforts resulted in the total synthesis of the glycosylated IL‐2 having full biological activity.     

Efficient Total Synthesis of Bongkrekic Acid and Apoptosis Inhibitory Activity of Its Analogues

Bongkrekic acid (BKA), isolated from the bacterium Burkholderia cocovenenans, is an inhibitor of adenine nucleotide translocator, which inhibits apoptosis, and is thus an important tool for the mechanistic investigation of apoptosis. An efficient total synthesis of BKA has been achieved by employing a three‐component convergent strategy based on Kocienski–Julia olefination and Suzuki–Miyaura coupling. It is noteworthy that segment B has been prepared as a new doubly functionalized coupling partner, which contributes to shortening of the number of steps. Torquoselective olefination with an ynolate has also been applied for the efficient construction of an unsaturated ester. Furthermore, it is revealed that 1‐methyl‐2‐azaadamantane N‐oxyl is an excellent reagent for final oxidation to afford BKA in high yield. Based on the total synthesis, several BKA analogues were prepared for structure–activity relationship studies, which indicated that the carboxylic acid moieties were essential for the apoptosis inhibitory activity of BKA. More easily available BKA analogues with potent apoptosis inhibitory activity were also developed.     

Polymerization initiated by the charge-transfer complex of styrene and maleic anhydride in the presence of cumene and of cumene and liquid sulfur dioxide

A polymerization was induced with a charge-transfer type of complex consisting of styrene and maleic anhydride in the presence a solvent such as ethyl benzene, cumene, or p-cymene. No polymer was obtained either when the solvent was missing from the polymerization system or when benzene, toluene, or xylene, which are relatively stable to hydrogen abstraction, was added to the polymerization system. An effective initiation, however, took place when cumene or p-cymene, each of which has a labile hydrogen on an α carbon, was added. On the basis of elementary analysis and infrared spectroscopy the formation of copolymer containing substantially equimolar amounts of styrene and maleic anhydride was ascertained. This polymerization was inhibited by the addition of DPPH, suggesting that the system styrene–maleic anhydride–cumene functions much as a conventional free-radical initiator. On the other hand, when a solution of cumene and liquid sulfur dioxide was added to the polymerization system, polystyrene was obtained. This polymerization was inhibited by the addition of a base such as dimethyl-formamide or dimethyl sulfoxide, indicating that the polymerization proceeds through carbonium ion intermediates. The addition of ethyl benzene or of p-cymene brought about the same result as cumene. It is conceivable that the polymerization is induced by the abstraction of hydrogen attached at the α position of cumene by means of the charge-transfer complex of styrene and maleic anhydride.     

Every Graph Is an Integral Distance Graph in the Plane

We prove that every finite simple graph can be drawn in the plane so that any two vertices have an integral distance if and only if they are adjacent. The proof is constructive.     

Maxwell speed distribution and analogue Hawking–Unruh temperature in an ontological model of a Harmonic oscillator ground state

Within an ontological (hidden variable) model of quantum fluctuation, one can discuss the actual   properties of a system regardless (independent) of measurement. Here we apply an ontological model proposed earlier to investigate a Harmonic oscillator in the quantum mechanical ground state. We first show that the actual speed of the oscillator fluctuates randomly following the Maxwell–Boltzmann distribution. On the other hand, the actual energy obeys a broad Gamma distribution with an average 3?ω/2$3?\omega /2$, where ω$\omega$ is the classical angular frequency, so that one may conclude that the outcome of a single energy measurement reveals the average of the actual energy. The distribution of actual speed (energy) thus formally resembles the distribution of speed (energy) of an ideal gas in thermal equilibrium of temperature T_g=?ω/2$T_g=?\omega /2$. We shall then argue that T_g$T_g$ can be written in a form analogous to the Hawking temperature for a Schwarzschild black hole in which the average distance of the oscillator from the origin plays the analogous role of the radius of the black hole event horizon. It can also be written in a form analogous to the Unruh temperature experienced by a body moving with a uniform acceleration. In the analogy, the oscillator suffers an effective acceleration which balances the attractive force of the trapping Harmonic potential, thus keeps its average position away from the origin.     

Vertex‐disjoint cycles containing specified vertices in a bipartite graph

A minimum degree condition is given for a bipartite graph to contain a 2‐factor each component of which contains a previously specified vertex. © 2004 Wiley Periodicals, Inc. J Graph Theory 46: 145–166, 2004     

SH-wave in a cylindrically anisotropic solid

Propagation of a transient SH-wave in a cylindrically anisotropic elastic solid is considered and an exact closed form solution for a special class of anisotropy is obtained. This is a case where a square root of the shear rigidity ratio is an integer. In this case we find an interesting wave pattern. However, the singularity at the wave front is of the same order as the one in the isotropic solid.     

Biodegradations of block copolymers composed of L- or D,L-lactide and six-membered cyclic carbonates prepared with organolanthanide initiators

Diblock copolymerizations of L - or D,L -lactide (LA) with trimethylene carbonate (TMC) or 2,2-dimethyltrimethylene carbonate (2,2-DTMC) with SmMe(C₅Me₅)₂-(tetrahydrofuran) as an initiator and triblock copolymerizations of L - or D,L -LA/cyclic carbonates/L - or D,L -LA with [Sm(C₅Me₅)₂]₂(PhCCCCPh) as an initiator generated the desired block copolymers. This article describes the comparison of biodegradabilities by proteinase K and a compost and mechanical properties between the resulting di- or triblock copolymers and random copolymers composed of L - or D,L -LA and cyclic carbonates. The scanning electron microscopic profiles of resulting polymers were measured to understand the morphological change during biodegradation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3572–3588, 2003     

Bioaccumulation of arsenic and its fate in a freshwater food chain

Accumulation, biomethylation and excretion of arsenic by an autotrophic freshwater alga, and the transport and transformation of the arsenic in the freshwater food chain [alga (autotroph)-moina (planktonic grazer) or shrimp (herbivore)-guppy (carnivore)] were investigated. These experimental results lead to the conclusion that total arsenic concentrations in organisms after accumulation from foods decreased one order of magnitude per elevation of the trophic level and biomethylation of the arsenic increased successively with an elevation in the trophic level. Predominant methylated arsenic species in moina and guppy were dimethyl- and trimethyl-arsenic compounds, respectively. Shrimp accumulated dimethyl- and trimethyl-arsenic compounds in nearly equivalent quantities. No or little monomethylarsenic compound was detected either in herbivores or carnivores.