Investigation of ring-opening polymerization of 5-[2-{2-(2-methoxyethoxy)ethoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one by organometallic catalysts

To develop new polymer-based materials, the design of aliphatic carbonate has received attention and become a well-known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM-MOE3OM, were typically prepared via ring-opening polymerization (ROP) using amidine-based catalysts such as 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know-how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)-type cyclen chelating with a metal-core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM-MOE3OM upon steadily degree of polymerization.     

The Kinetic Stability of Cationic Benzyl Titanium Complexes that Contain a Linked Amido-Cyclopentadienyl Ligand: The Influence of the Amido-Substituent on the Ethylene Polymerization Activity of “Constrained Geometry Catalysts”

Cationic benzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')-(CH₂Ph)]⁺ were cleanly formed by the reaction of the dibenzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')(CH₂Ph)₂] with B(C₆F₅)₃ and [Ph₃C][B(C₆F₅)₄] in bromobenzene. NMR spectroscopic studies suggest that the benzyl titanium cations contain a fluxional η²-coordinated benzyl ligand. Kinetic analysis showed that the benzyl titanium cations decompose according to first-order kinetics and that the amido substituents R' (R' = Me, ⁱPr, ^tBu) in the linked amido-cyclopentadienyl ligand influence the lability of these benzyl titanium cations. The order of the kinetic stability of the benzyl titanium cations was found for both anions to follow the order R' = Me > ⁱPr > ^tBu. The benzyl titanium cations generated with [Ph₃C][B(C₆F₅)₄] were found to undergo faster decomposition than those generated with B(C₆F₅)₃. The ethylene polymerization activity order for both systems was found to be the reverse: R' = ^tBu > ⁱPr > Me. The decomposition of the benzyl titanium cations was suggested to occur via C—H activation with concomitant toluene elimination.     

Kinetic roughening transition and missing regime transition of melt crystallized polybutene-1 tetragonal phase: growth kinetics analysis

The morphology and lateral growth rate of isotactic polybutene-1 (it-PB1) have been investigated for crystallization from the melt over a wide range of crystallization temperatures from 50 to 110°C. The morphology of it-PB1 crystals is a rounded shape at crystallization temperatures lower than 85°C, while lamellar single crystals possess faceted morphology at higher crystallization temperatures. The kinetic roughening transition occurs around 85°C. The nucleation and growth mechanism for crystallization does not work below 85°C, since the growth face is rough. However, the growth rate shows the supercooling dependence derived from the nucleation and growth mechanism. The nucleation theory seems still to work even for rough surface growth. Possible mechanisms for the crystal growth of this polymer are discussed.     

Smart polyion complex micelles for targeted intracellular delivery of PEGylated antisense oligonucleotides containing acid-labile linkages

A novel pH-sensitive and targetable antisense ODN delivery system based on multimolecular assembly into polyion complex (PIC) micelles of poly(L-lysine) (PLL) and a lactosylated poly(ethylene glycol)-antisense ODN conjugate (Lac-PEG-ODN) containing an acid-labile linkage (beta-propionate) between the PEG and ODN segments has been developed. The PIC micelles thus prepared had clustered lactose moieties on their peripheries and achieved a significant antisense effect against luciferase gene expression in HuH-7 cells (hepatoma cells), far more efficiently than that produced by the nonmicelle systems (ODN and Lac-PEG-ODN) alone, as well as by the lactose-free PIC micelle. In line with this pronounced antisense effect, the lactosylated PIC micelles showed better uptake than the lactose-free PIC micelles into HuH-7 cells; this suggested the involvement of an asialoglycoprotein (ASGP) receptor-mediated endocytosis process. Furthermore, a significant decrease in the antisense effect (27 % inhibition) was observed for a lactosylated PIC micelle without an acid-labile linkage (thiomaleimide linkage); this suggested the release of the active (free) antisense ODN molecules into the cellular interior in response to the pH decrease in the endosomal compartment is a key process in the antisense effect. Use of branched poly(ethylenimine) (B-PEI) instead of the PLL for PIC micellization led to a substantial decrease in the antisense effect, probably due to the buffer effect of the B-PEI in the endosome compartment, preventing the cleavage of the acid-labile linkage in the conjugate. The approach reported here is expected to be useful for the construction of smart intracellular delivery systems for antisense ODNs with therapeutic value.     

Evolution of long-period stacking ordered structures on annealing as-cast Mg85Y9Zn6 alloy ingot observed by synchrotron radiation small-angle scattering

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Study on cracking in electron beam welding of A6061 (Al‐Si‐Mg alloy)

Electron beam surfacing in an electron accelerator using powder mixtures of chromium carbides with boron carbide in different weight ratios and with different radiation parameters was used to produce wear- and corrosion-resisting coatings. It is shown that there are compositions of the surfacing mixtures and conditions of electron beam effect ensuring maximum values of wear and corrosion resistance.     

Application of the Antibody-Inducing Activity of Glycosphingolipids to Human Diseases

Glycosphingolipids (GSLs) are composed of a mono-, di-, or oligosaccharide and a ceramide and function as constituents of cell membranes. Various molecular species of GSLs have been identified in mammalian cells due to differences in the structures of oligosaccharides. The oligosaccharide structure can vary depending on cell lineage, differentiation stage, and pathology; this property can be used as a cell identification marker. Furthermore, GSLs are involved in various aspects of the immune response, such as cytokine production, immune signaling, migration of immune cells, and antibody production. GSLs containing certain structures exhibit strong immunogenicity in immunized animals and promote the production of anti-GSL antibodies. By exploiting this property, it is possible to generate antibodies that recognize the fine oligosaccharide structure of specific GSLs or glycoproteins. In our study using artificially synthesized GSLs (artGSLs), we found that several structural features are correlated with the antibody-inducing activity of GSLs. Based on these findings, we designed artGSLs that efficiently induce the production of antibodies accompanied by class switching and developed several antibodies that recognize not only certain glycan structures of GSLs but also those of glycoproteins. This review comprehensively introduces the immune activities of GSLs and their application as pharmaceuticals.