Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. II. Catalysts for stereospecific polymerization of butadiene to syndiotactic 1,2-polybutadiene

Butadiene is polymerized by cobalt compound–organoaluminum–CS₂ catalysts to give highly crystalline syndiotactic 1,2-polybutadiene (s-PB) having melting point up to 216°C. An aluminum-free catalyst, Co(C₄H₆)(C₈H₁₃)-CS₂, is also effective. Syndiotactic polymerization with Co(C₄H₆)(C₈H₁₃)-CS₂ is not interrupted by the addition of protic substances such as water and alcohol, but is influenced by donor or acceptor substances. The donor molecule, e.g., dimethylsulfoxide or dimethylformamide, decreases the stereoregularity, i.e., syndiotacticity and 1,2 content. An acceptor molecule of organoaluminum with appropriate acidity such as AlEt₃-AlEt₂Cl or tetraethylaluminoxane increases the molecular weight, stereoregularity, and yield of the polymer. In the presence of CS₂ a mixture of cis-PB and s-PB was obtained by using Co(octoate)₂-AlEt₂Cl-H₂O, with molar ratio H₂O/Co less than unity. In the case of H₂O/Co > 1, only cis-PB was obtained. By the addition of donor substances such as ester, ether, nitrile, and AlEt₃, s-PB was obtained even when H₂O/Co > 1. The amount and ratio of cis-PB and s-PB are dependent upon the nature and amount of the additives.     

Vibrational energy redistribution in jet-cooled hydrogen-bonded phenols

Dispersed fluorescence spectra of jet-cooled hydrogen-bonded phenols have been observed by excitation of intra- and inter-molecular vibrational levels. The spectra show that vibrational energy redistribution occurs from the excited vibronic level into intermolecular vibrational modes. Energy redistribution within the intermolecular vibrational modes was also found.     

Polymerization of vinyl monomers in the water–1,4-dioxane system containing peroxide and water-soluble polymer

Water-solube polymer (PST) containing triethylenetetramine side chain was prepared by the amination of chloromethylated polystyrene with triethylenetetramine in 1,4-dioxane. The polymerization of vinyl monomers was carried out in the water–organic solvent system containing PST and a very small amount of peroxide. The polymerization of methyl methacrylate proceeded smoothly in the presence of both peroxide and PST. It was found that the polymerization was initiated with the radicals generated by the interaction between hydroperoxide and amino groups of PST. 1,4-Dioxane hydroperoxide showed a high activity for the polymerization of methyl methacrylate. The maximum rate of the polymerization was observed at 60°C and in an approximately neutral solution. The addition of suitable amount of Cu(II) accelerated the polymerization of methyl methacrylate. The selective polymerization of vinyl monomers was observed in this system.     

Desulfonylation of poly(4‐hydroxystyrene sulfone) by vapor phase silylation

Vapor phase silylation of poly(4‐hydroxystyrene sulfone) (PHOSS) film was carried out with (trimethylsilyl)dimethylamine (TMSDMA) as a silylation reagent. Infrared spectroscopy was used to follow the silylation. Phenolic hydroxyl groups were trimethylsilylated, but desulfonylation of PHOSS was greatly enhanced simultaneously. The reaction rates were investigated at reaction temperatures of 50, 60, and 70°C. The rate of silylation increased with increasing reaction temperature. However, the rate of desulfonylation was very fast in the presence of TMSDMA and was virtually invariant with reaction temperature. It was confirmed that trimethylsilylation in the polymer side chain of PHOSS enhanced desulfonylation in the main chain. Trimethylsilylation might be expected to lower the ceiling temperature of the polymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1549–1554, 1999     

Decomposition of poly(4‐hydroxystyrene sulfone) in alkaline aqueous solutions

It was confirmed by ¹H NMR measurements that poly(4‐hydroxystyrene sulfone) (PHOSS) was decomposed in dissolving in a deuterium oxide solution of sodium deuteroxide to give trans‐2‐(4‐hydroxyphenyl)ethenesulfinic acid (HESA) and 4‐hydroxystyrene (HOSt) quantitatively. HESA and HOSt were formed in the mole ratio of about 2:3. The amount of each product was almost independent of the alkaline concentration ranging from 1 to 12 w/v %. The mole ratio of monomeric units of decomposed PHOSS to NaOD was estimated to be 0.64. A possible decomposition mechanism was discussed. The initiation reaction was the abstraction of a methylene proton anti to a sulfonyl group by alkali, followed by the main chain scission of the polymer. The resonance structure stabilizing a terminal phenolate anion possibly enhanced the elimination of HESA, so that it was produced in quantity comparable to HOSt. The decomposition of PHOSS in alkaline aqueous solutions was a conformation‐determined polymer degradation following Hofmann's rule. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2760–2766, 2000     

Urinary metabolic profile of phenylketonuria in patients receiving total parenteral nutrition and medication

Nutrition and drugs are main environmental factors that affect metabolism. We performed metabolomics of urine from an 8‐year‐old patient (case 1) with epilepsy and an 11‐year‐old patient (case 2) with malignant lymphoma who was being treated with methotrexate. Both patients were receiving total parenteral nutrition (TPN). We used our diagnostic procedure consisting of urease pretreatment, partial adoption of stable isotope dilution, gas chromatography/mass spectrometry (GC/MS) measurement and target analysis for 200 analytes including organic acids and amino acids. Surprisingly, their metabolic profiles were identical to that of phenylketonuria. The neopterin level was markedly above normal in case 1, and both neopterin and biopterin were significantly above normal in case 2. Mutation analysis of genomic DNA from case 1 showed neither homozygosity nor heterozygosity for phenylalanine hydroxylase deficiency. The metabolic profiles of both cases were normal when they were not receiving TPN. TPN is presently prohibited for individuals who have inherited disorders that affect amino acid metabolism. Although the Phe content of the TPN was not the sole cause of the PKU profile, its effect, combined with other factors, e.g. specific medication or possibly underlying diseases, led to this metabolic abnormality. The present study suggests that GC/MS‐based metabolomics by target analysis could be important for assuring the safety of the treatments for patients receiving both TPN and methotrexate. Metabolomic profiling, both before and during TPN, is useful for determining the optimal nutritional formula not only for neonates, but also for young children who are known heterozygotes for metabolic disorders or whose status is unknown. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3‐triazol and benzoxazine groups in the main chain by a step‐growth click‐coupling reaction

The click‐coupling reaction was applied to polycondensation, to synthesize a high‐molecular weight prepolymer having benzoxazine moieties in the main chain. For the polycondensation, a bifunctional N‐propargyl benzoxazine was synthesized from bisphenol A, propargylamine, and formaldehyde. The propargyl group was efficiently used for the copper(I)‐catalyzed alkyne‐azide “click” reaction with p‐xylene‐α,α′‐diazide, to give the corresponding linear polycondensate having 1,2,3‐triazole junctions. The polycondensation proceeded in N,N‐dimethylformamide (DMF) at room temperature. By this highly efficient “click‐” polycondensation reaction, the benzoxazine ring in the monomer was successfully introduced into the polymer main chain without any side reaction. The obtained polymer (=prepolymer) underwent thermal crosslinking to afford the corresponding product, which was insoluble in a wide range of organic solvents and exhibited higher thermal stability than the polymer before crosslinking. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2316–2325, 2008     

The analysis of N-glycolylneuraminic acid(NeuGc) of hepatoma tissue and K562 cell ferritins using HPLC and mass spectrometry

Ferritin is an iron-storage protein and its serum level is known to increase in the patient of with inflammation and malignant tumor. To further elucidate the difference between ferritins from normal human liver tissue and that of cancer cells, their sialic acids were analyzed. The Western blot analysis and the cytochemical staining using anti-NeuGc antiserum indicated that ferritins from the human hepatocarcinoma tissue and malignant K562 cells contain NeuGc, but that from the normal liver does not. The result was also confirmed by HPLC analysis and MALDI-TOF/MS analysis of sialic acids which were derivatized by the DMB method. It was also shown that the sialic acid content in hepatocarcinoma ferritin was much higher than that in the normal liver ferritin. These results suggest that normal and cancerous liver ferritins are qualitatively and quantitatively different in sialylation. In addition, K562 cells were shown to express NeuGc even if the cells were cultured in serum-free media which lack NeuGc. This is of interest from the current concept that expression of NeuGc in human cells is due to uptake and utilization of exogenous NeuGc.     

Instability of the 2S electron bubbles

The 2S electron bubble placed in liquid helium has been previously believed to be spherical. We show that the 2S bubble is morphologically unstable at pressures above -1.23 bars. The 2S state being known to be radially unstable at pressures below -1.33 bars, the result leaves only a very narrow pressure range in which it can be found in a spherical configuration. Our stability analysis indicates that the 2S bubble is unstable against perturbations proportional to any of the third spherical harmonics Y(3m). Our numerical simulations show that there exist nonspherical stable configurations, such as the ones Maris and Konstantinov predicted for the 1P, 1D, and 2P electron bubbles and confirmed experimentally for the 1P. We believe that the 2S bubbles can also be produced and that our prediction will yield itself to experimental verification.