Resin-supported acid- and base-catalyzed one-pot sequential reaction including an enantioselective step

One-pot sequential acidic deacetalization and basic enantioselective aldol reaction were realized using Amberlite IR-120 (H⁺-form) and a resin-supported peptide catalyst, and the reusability of the catalysts was demonstrated.     

Asymmetric Total Synthesis of (+)‐Ryanodol and (+)‐Ryanodine

(+)‐Ryanodine ( 1 ) is the ester derivative of 1H‐pyrrole‐2‐carboxylic acid and the complex terpenoid (+)‐ryanodol ( 2 ), which possesses eleven contiguous stereogenic centers on the ABCDE‐ring system. Compound 1 is known to be a potent modulator of intracellular calcium release channels, whereas the activity of 2 is significantly weaker. To chemically construct 1 , the multiple oxygen functional groups must be installed on the fused pentacycle in stereoselective fashions and the extremely hindered C3‐hydroxy group must be acylated in a site‐selective manner. First, the total synthesis of 2 was accomplished by introducing the five stereocenters from the previously prepared enantiopure ABDE‐ring 7 . Stereoselective construction of the C3‐secondary, C2‐ and C6‐tertiary alcohols was achieved by three nucleophilic reactions. The C9‐ and C10‐trisubstituted carbon centers were regio‐ and stereoselectively introduced by hydroboration/oxidation of the six‐membered C‐ring, which was formed by the ring‐closing metathesis reaction. Direct esterification of the C3‐alcohol with pyrrole‐2‐carboxylic acid proved unsuccessful; therefore, we developed a new, two‐step protocol for attachment of the pyrrole moiety. The C3‐hydroxy group was first converted into the less sterically cumbersome glycine ester, which was then transformed into the pyrrole ring through condensation with 1,3‐bis(dimethylamino)allylium tetrafluoroborate. This procedure resulted in the first total synthesis of 1 .     

Effective form of sulfoquinovosyldiacyglycerol (SQDG) vesicles for DNA polymerase inhibition

Sulfoquinovosyldiacyglycerol (SQDG) has a wide range of biological activities that make it an attractive compound for the development of new drugs. Chemically synthesized beta-SQDG-C(18:0) (1,2-di-O-stearoyl-3-O-(6-deoxy-6-sulfo-beta-d-glucopyranosyl)-sn-glycerol), for example, has a potent inhibitory effect on DNA polymerases. We investigated the properties of the vesicle form of beta-SQDG-C(18:0) as the monomer has low solubility in water. The structure of the beta-SQDG-C(18:0) vesicles are highly influenced by NaCl concentration in preparation process. At low NaCl concentrations, the beta-SQDG-C(18:0) vesicles have high surface curvature and form small unilamellar vesicles. Increases in NaCl concentration, resulted in decreased surface curvature and a tendency for beta-SQDG-C(18:0) to form large multilamellar vesicles. The small unilamellar vesicles showed a potent inhibitory effect on DNA polymerase beta, whereas the large multilamellar vesicles had no such effect. We investigated further the relationship between vesicle size and activity by preparing smaller vesicles (262, 99 and 43 nm in diameter) using an extrusion technique. These smaller vesicles had a greater inhibitory effect on DNA polymerase beta activity than non-extruded vesicles. beta-SQDG-C(18:0) vesicles, especially those of small size, were effective in DNA polymerase inhibition and are expected to have high applicability in DNA polymerase study.     

A Novel Layered Silicate with a Helical Morphology

Helices composed of stacked layers are present in the novel silicate obtained from a silica sol and NaOH by hydrothermal synthesis in the presence of tetramethylammonium (TMA) hydroxide and 1,4-dioxane. The helical morphology is evident in scanning electron micrographs (see picture). The TMA and sodium ions of the silicate are readily replaced by protons, and on heating to 200°C a reversible phase transition occurs in which water molecules are lost from between the layers.     

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.     

Synthesis of protein-silica hybrid hollow particles through the combination of protein catalysts and sonochemical treatment

Hollow spherical particles with protein-silica hybrid shell structures have been synthesized through a combination of the catalytic activity of the protein and sonochemical treatment; the morphologies of the particles were controlled by varying the protein concentration.     

Performance of a genetic algorithm for the graph partitioning problem

The performance of the genetic algorithm (GA) for the graph partitioning problem (GPP) is investigated by comparison with standard heuristics on well-known benchmark graphs. In general, there is a case where a practical performance of a conventional genetic approach, which performs only simple operations without a local search strategy, is not sufficient. However, it is known that a combination of GA and local search can produce better solutions. From this practice, we incorporate a simple local search algorithm into the GA. In particular, the search ability of the GA is compared with standard heuristics such as multistart local search and simulated annealing, which use the same neighborhood structure of the simple local search, for solving the GPP. Experimental results show that the GA performs better than its competitors.     

A simple purely infinite <Emphasis Type="Italic">C</Emphasis>*-algebra associated with a lambda-graph system of the Motzkin shift

The Motzkin shift is a nonsofic subshift consisting of the four brackets (,[,),] with standard bracket rule and one additional symbol, the unit 1. We show that the C*-algebra associated with a -graph system that presents the Motzkin shift is simple and purely infinite. It is generated by two partial isometries and three isometries, and is a universal unique C*-algebra subject to some operator relations among the generators. The K₀-group of the C*-algebra is computed to be the abelian group of all -valued continuous functions on the Cantor set. The K₁-group is trivial. Hence it is not stably isomorphic to any Cuntz-Krieger algebra and to any Cuntz-algebra.Mathematics Subject Classification (2000): 46L80, 46L55, 37B10in final form: 6 October 2003     

Bowen–Franks Groups for Subshifts and Ext-Groups for C*-Algebras

We generalize the Bowen–Franks groups for topological Markov shifts to general subshifts as the Ext-groups for the associated C ^*-algebras. The generalized Bowen–Franks groups for subshifts are shown to be invariant under flow equivalence and, hence, invariant under topological conjugacy. They are regarded as the indices of Fredholm operators related to extensions of the associated C ^*-algebras so that they are described in terms of symbolic dynamical systems. In particular, the group for a sofic subshift is determined by the adjacency matrix of its left Krieger cover graph. The Bowen–Franks groups for some non sofic subshifts are calculated, proving that certain subshifts with the same topological entropy are not flow equivalent.