Reaction of oligomethylene di(3-oxobutanoate) with 1,1-disubstituted alkenes and molecular oxygen in the presence of manganese(II and/or IE) acetate

The reactions of 1,1-disubstituted ethenes with oligomethylene di(3-oxobutanoate) in the presence of manganese(II and/or III) acetate and atmospheric oxygen yielded an ω-(3-oxobutanoyloxy)alkyl 6,6-diaryl-3-hydroxy-3-methyl-1,2-dioxane-4-carboxylate, oligomethylene di(6,6-diaryl-3-hydroxy-3-methyl-1,2-dioxane-4-carboxylate)s, ω-hydroxyalkyl 6,6-diaryl-3-hydroxy-3-methyl-1,2-dioxane-4-carboxylates, an ω-(3-oxobutanoyloxy)alkyl 5,5-diaryl-2-methyl-4,5-dihydrofuran-3-carboxylate, oligomethylene di(5,5-diaryl-2-methyl-4,5-dihydrofuran-3-carboxylate)s, ω-hydroxyalkyl 5,5-diaryl-2-methyl-4,5-dihydrofuran-3-carboxylates, and an ohgomethylene diester bearing a substituted 1,2-dioxane ring and a substituted 4,5-dihydrofuran ring. The reaction of the 1,2-dioxan-3-ols with acid gave the corresponding compounds bearing furan rings. The reaction of 1,1,6,6-tetraaryl-1,5-hexadienes with oligomethylene di(3-oxobutanoate) in the presence of manganese(III) acetate yielded macrocyclic diesters bearing two 4,5-dihydrofuran rings.     

Preparation,properties and reactivities of novel platinum compounds containing a thiomethoxymethyl group

Oxidative addition of ClCH₂SCH₃ to PtL₄ afforded trans-PtL₂(CH₂SCH₃)Cl (Ia, L = Ph₃P;Ib, L = MePh₂P). Treatment of I with NH₄PF₆ or Et₃OBF₄ in CH₂C1₂ gave ionic species, [PtL₂(CH₂SCH₃)]X (II, L = Ph₃P, MePh₂P, X = BF₄, PF₆), while similar treatment with MeSO₃F in benzene yielded a new type of stable dimethylsulfonium methylide—platinum complex, trans-[PtL₂(CH₂SMe₂)Cl] SO₃F (IIIa, L = Ph₃P; IIIb, L = MePh₂P). Action of H₂O₂ on Ia gave [Pt(Ph₃P)(μ-CH₂SCH₃)C1]₂ (IV) and its triphenylarsine analog, [Pt(Ph₃As)(μ-CH₂SCH₃)C1]₂ (V) was prepared in one step by oxidative addition of ClCH₂SCH₃ to Pt(AsPh₃)₄. The structural difference between [Pt(Ph₃P)(μ-CH₂SCH₃)C1]₂ and Pd(Ph₃P)- (CH₂SCH₃)C1 is discussed in terms of the difference in the ionization potential from d¹⁰ to d⁸ electronic state of metals.     

Polyhydrazides. IV. Preparation and properties of poly-N-ethyl- and isopropylhydrazide oxadiazoles

High molecular weight poly-N-alkylhydrazide-oxadiazoles have been prepared in poly-phosphoric acid by alkylation of poly-1,3,4-oxadiazole which was synthesized from terephthalic acid and hydrazine sulfate. Various kinds of reagents having an alkoxy group were used as alkylating agent, and N-ethylated and N-propylated polyhydrazides containing oxadiazole units were obtained. The thermal properties of the polymers obtained were investigated by using infrared spectroscopy, viscometry, differential thermometric and thermogravimetric techniques. Soluble poly-N-alkylhydrazide-oxadiazole are thermally cyclized to poly-1,3,4-oxadiazole with elimination of olefins and water at 226–330°C for propylated polydrazide and at 240–360°C for ethylated polyhydrazide. For both, weight loss in polyhydrazides occurs in two distinct stages corresponding, respectively, to cyclization and decomposition of the poly-1,3,4-oxadiazole formed in situ.     

Plasma-polymerized allylamine film used as a new solid phase in immunoradiometric assay (IRMA): effect of antibody (F(ab')2 fragment) concentration on dose response in two-site IRMA.

Allylamine (ALAM) film was plasma-polymerized on a flat glass (referred to as ALAM(GLA): GLA refers to a flat glass plate) for use as a solid phase in two-site immunoradiometric assay (two-site IRMA). Adsorption of F(ab')2 anti-human immunoglobulin G [formula: see text] to ALAM(GLA) was larger than adsorption on a polyvinyl chloride plate (referred to as PVC). Contrary to the expectation that the dose response for human IgG (hIgG) on ALAM (GLA) was better than that on PVC, the dose responses on both solid phases were the same. This phenomenon was independent of molecular size of the antigen (Ag) (hIgG or Fc fragment of hIg G (hIgG-Fc)) and also the reaction with protein A (pA). Because direct measurements of binding with 125I-labeled hIgG (hIgG*) or hIgG-Fc (hIgG-Fc*) showed no difference between ALAM(GLA) and PVC, the phenomenon was not due to the second step in the system of two-site IRMA (an Ag--Ab reaction (Ab refers to antibody)). These results indicated that the phenomenon was due to the first step (the adsorption of [formula: see text] to a solid phase). When the concentration of [formula: see text] immobilized on the solid phases was lowered, a significant increase in the dose response was observed for ALAM(GLA).     

Synthesis of 6-hydroxylated bile acids and identification of 3 alpha,6 alpha,7 alpha,12 alpha-tetrahydroxy-5 beta-cholan-24-oic acid in human meconium and neonatal urine

Three 6-hydroxylated bile acids, 3 alpha,6 alpha,7 alpha,12 alpha-, 3 alpha,6 beta,7 alpha,12 alpha- and 3 alpha,6 beta,7 beta,12 alpha-tetrahydroxy-5 beta-cholan-24-oic acids, were synthesized from methyl cholate, and a sensitive method was developed for analyzing them by gas chromatography-mass spectrometry for the stoichiometric study of fetal bile acids. 3 alpha,6 alpha,7 alpha,12 alpha-Tetrahydroxy-5 beta-cholan-24-oic acid (6 alpha-hydroxylated cholic acid) was identified from human meconium and healthy neonatal urine by comparison with the mass spectrum of the reference compound. In human meconium, 6 alpha-hydroxylated cholic and chenodeoxycholic acids were determined in 1.2% and 29.0% of the total bile acids, respectively. We discuss the significance of hydroxylation at the C-1 beta and C-6 alpha positions of bile acids and their elimination in fetal and neonatal periods.     

Synthesis of polymethacrylate derivatives having sulfated maltoheptaose side chains with anti‐HIV activities

Anti‐HIV (human immunodeficiency virus) active polymethacrylates having pendant sulfated oligosaccharides were synthesized, and the relationship between structures and biological activities of the polymethacrylates was examined. Acetylated 1‐O‐methacryloyl maltoheptaoside (MA‐AcM7) was polymerized with AIBN as an initiator to give polymethacrylates having a pendant acetylated maltoheptaose in every repeating unit, poly(MA‐AcM7)s. After hydroxyl groups were recovered by deacetylation, the polymethacrylates having maltoheptaose units, poly(MA‐M7)s, were sulfated to give polymethacrylates having sulfated maltoheptaose side‐chains, poly(MA‐SM7)s, with degrees of sulfation of 1.1 to 2.7 (maximum, 3.0). These polymethacrylates including sulfated oligosaccharides exhibited low anti‐HIV activities represented by the 50% protecting concentration (EC₅₀) in the range of 15–62 μg/mL and low blood anticoagulant activities around 10 unit/mg (standard dextran sulfate, 22.7 unit/mg). The anti‐HIV activity increased with increasing degree of sulfation to reach EC₅₀ of 15–16 μg/mL. In addition, copolymerization of MA‐AcM7 with methyl methacrylate (MMA) and subsequent sulfation gave polymethacrylates consisting of various proportions of highly sulfated maltoheptaose and MMA units. It was revealed that the anti‐HIV activity increased with decreasing proportion of the sulfated oligosaccharide moiety and that a copolymethacrylate having 22 mol % of sulfated maltoheptaose units (DS = 3.0) had a high anti‐HIV activity in the EC₅₀ of 0.3 μg/mL. The blood anticoagulant activity increased slightly from 9 to 18 unit/mg with decreasing proportion of the sulfated maltoheptaose units. These results suggested that the biological activities were influenced strongly by the spatial distance between sulfated oligosaccharide substituents in the polymethacrylate main chain. Distinction and conformation of the oligosaccharide side chains also played an important role. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 789–800, 1999     

Effects of Early Physical Therapist-supervised Walking on Clinical Outcomes after Liver Resection: Propensity Score Matching Analysis

Objective: The study aimed to demonstrate the significance of early postoperative physical therapy interventions on clinical outcomes by determining the influence of the distance walked under the supervision of a physical therapist in the early postoperative period after liver cancer. Methods: All consecutive patients who underwent surgery for liver cancer between April 2018 and March 2020 were eligible for enrollment in the study. The total walking distance during physical therapy till the third postoperative day was examined. The clinical outcomes comprised duration of postoperative hospital stay, time to independent walking, and occurrence of postoperative complications. For data analysis, the patients were divided into two groups: those who walked more than the median total distance (the long-distance group) and those who walked less than the median distance (the short-distance group). We used propensity score matching to match the background characteristics between the groups. Results: Of the 65 patients who were eligible, 14 patients were included in the two groups each, after matching. The long-distance walking group had a significantly shorter hospital stay (9.0 days vs. 11.0 days, p=0.008) and a shorter time to independent walking (3.5 days vs. 7.5 days, p=0.019) than the short-distance walking group. There were no significant differences in postoperative complications between the two groups (7.1% vs. 42.8%, p=0.08). Conclusion: In the early postoperative period after liver cancer surgery, increasing the walking distance under the supervision of a physical therapist is important for improving clinical outcomes. Further prospective studies are needed to confirm the findings of this study.     

Perylene-tetrapalladium sandwich complexes

Bis-perylene-tetrapalladium sandwich complexes are synthesized and structurally characterized. These are the first examples of bis-arene sandwich complexes having metal-metal bond chains. X-ray crystallographic analyses showed that the tetrapalladium chain is bound to perylene ligands at the C8 edge position.     

Lasing action of active-particles dispersed in microdroplets and its enhanced characteristics by highly scattering intralipid-10% mixture

The first laser action of active-particles of 1–2 m in diameter, red fluorescent-powder (FP), dispersed in nonactive (nonlasing) 100 m-sized liquid microdroplets is reported. Lasing characteristics of FP-containing microdroplets by mixing Intralipid-10% as highly scattering turbid media are also described. Well-defined lasing thresholds can be confirmed from the FP-dispersed pure microdroplets, and lowered lasing threshold along with enhanced lasing emission is achieved by appropriately mixing the Intralipid-10% solution. Lasing threshold in these microdroplets can be determined not through the spectral narrowing features but through the input–output data. We believe that these new microdroplet configurations offer one of the new categories of lasing media and they seem also to simulate to some biological pigments or organelles contained in cells and small tissues.     

Combinatorial Classification of Optimal Authentication Codes with Arbitration

Unconditionallysecure authentication codes with arbitration ( A ²-codes)protect against deceptions from the transmitter and the receiveras well as that from the opponent. We first show that an optimalA ²-code implies an orthogonal array and an affine-resolvable design. Next we define a new design,an affine -resolvable + BIBD,and prove that optimal A ²-codes are equivalentto this new design. From this equivalence, we derive a conditionon the parameters for the existence of optimal A ²-codes.Further, we show tighter lower bounds on the size of keys thanbefore for large sizes of source states which can be consideredas an extension of the bounds on the related designs.