Total Synthesis and Structure Elucidation of JBIR‐39: A Linear Hexapeptide Possessing Piperazic Acid and γ‐Hydroxypiperazic Acid Residues

The total synthesis and stereochemical structural elucidation of JBIR‐39, containing four nonproteinogenic piperazic acid (Piz) residues, is reported. The synthesis includes Sc(OTf)₃‐catalyzed acylation of a Piz(γ‐OTBS) derivative with piperazic acid chloride, providing the desired Piz‐Piz(γ‐OTBS) dipeptide in high yield without epimerization. After assembling two additional Piz moieties and (S)‐isoleucic acid at the N‐terminus, amidation with the (R)‐α‐methylserine ester at the C‐terminus, and deprotection afforded the desired (2R,8S)‐hexapeptide, which is the assumed structure of JBIR‐39. Although the spectral data of the (2R,8S)‐hexapeptide was not identical to JBIR‐39, further synthesis of three stereoisomers confirmed the stereochemical structure of JBIR‐39 to be (2S,6S,8S,11R,16S,21R,26S,27S).     

Representations of inverse functions

Let be an arbitrary map from an abstract set into an abstract set . We shall use the theory of reproducing kernels to provide a general method for representing the inverse map in terms of . We give several concrete examples of this method.

     

Cutting Plane/Tabu Search Algorithms for Low Rank Concave Quadratic Programming Problems

In this paper, we will propose an efficient heuristic algorithm for solving concave quadratic programming problems whose rank of the objective function is relatively small. This algorithm is a combination of Tuy's cutting plane to eliminate the feasible region and a kind of tabu-search method to find a good vertex. We first generate a set of V of vertices and select one of these vertices as a starting point at each step, and apply tabu-search and Tuy's cutting plane algorithm where the list of tabu consists of those vertices eliminated by cutting planes and those newly generated vertices by cutting planes. When all vertices of the set V are eliminated, the algorithm is terminated. This algorithm need not converge to a global minimum, but it can work very well when the rank is relatively small (up to seven). The incumbent solutions are in fact globally optimal for all tested problems. We also propose an alternative algorithm by incorporating Rosen's hyperrectangle cut. This algorithm is more efficient than the combination of Tuy's cutting plane and tabu-search.     

Solutions of Tikhonov Functional Equations and Applications to Multiplication Operators on Szegö Spaces

We consider a natural representation of solutions for Tikhonov functional equations. This will be done by applying the theory of reproducing kernels to the approximate solutions of general bounded linear operator equations (when defined from reproducing kernel Hilbert spaces into general Hilbert spaces), by using the Hilbert–Schmidt property and tensor product of Hilbert spaces. As a concrete case, we shall consider generalized fractional functions formed by the quotient of Bergman functions by Szegö functions considered from the multiplication operators on the Szegö spaces.     

ASACUSA MUSASHI: New progress with intense ultra slow antiproton beam

Our group “ASACUSA MUSASHI” has established an efficient way for accumulating antiprotons and extracting them as intense ultra-slow mono-energetic beams at the CERN-AD facility. This novel beam opens new frontiers for investigating a variety of physics. For realizing H? spectroscopy and the test for charge-parity-time symmetry, we have also developed the cusp trap, a combination of an anti-Helmholz superconducting coil and a multi-ring electrode trap, for trapping both antiprotons and positrons and then synthesizing antihydrogens. Recently, the cusp trap was practically used to accumulate antiprotons. The last piece for synthesizing antihydrogens in the cusp trap is the positron accumulator. We have developed a compact system to effectively accumulate positrons based on N₂ gas-buffer scheme with a specially designed high precision cylindrical multi-ring electrode trap. The recent progress of the developing work is an important milestone for upcoming antihydrogen science of ASACUSA MUSASHI.     

Pressurized liquid extraction of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and coplanar polychlorinated biphenyls from contaminated soil

Extraction solvents for pressurized liquid extraction (PLE) used to extract polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/PCDFs), and coplanar polychlorinated biphenyls (Co-PCBs) from contaminated soil were investigated. The PCDD/PCDFs and Co-PCBs in Certified Reference Material: CRM 0422 (Forest soil) were extracted using toluene, n-hexane, acetone, acetone/toluene and acetone/n-hexane (1:1, v/v). Soxhlet extraction was the reference method. Results demonstrated that PLE using mixed solvents produced better analyte recoveries than the single solvents. However, these results were lower than those for Soxhlet extraction. Additional extraction cycles using mixed solvents achieved better recovery results. Mixed solvents and several extraction cycles were necessary for satisfactory extraction of more tightly bound PCDD/PCDFs and Co-PCBs from soil.     

Deposition of mechanically hard amorphous carbon nitride films from decomposition of BrCN. Effects of substrate cooling and pulsed rf-bias voltage

Mechanically hard amorphous carbon nitride films were formed by applying a combination of radio frequency (RF) bias voltage to the substrate and the chemical vapor deposition process using the decomposition reaction of BrCN with the microwave discharge flow of Ar. Cooling water was circulated inside the substrate stage. The maximum hardness was (17 ± 1) GPa for the film prepared under the negative RF bias voltage, −V_RF, of 30 V. This hardness was nearly twice that of the film prepared without cooling, suggesting that substrate cooling was effective for suppressing the relaxation of the internal stress of the film due to the temperature rise during the application of the RF bias voltage. Under the continuous operation of the RF bias voltage, films cannot be formed for −V_RF > 40 V because of the sputtering by the bombardment of energetic Ar⁺. Then, the RF bias voltage was applied with a pulsed operation. By using this operation films were prepared in the range of −V_RF = 40-100 V. The hardness, (36 ± 10) GPa, was obtained for the film obtained under the conditions of −V_RF = 100 V, the pulse period of 1000 s, and the pulse-on time of 800 s. The observed hardness scattered largely for the different observation points within this film; a single observation point in that film showed the maximum hardness of 46 GPa. According to the IR spectra of the films, the three-dimensional C-N network structure was developed.