Efficient construction of the hexacyclic ring core of palau'amine: the pKa concept for proceeding with unfavorable equilibrium reactions

Palau''amine has received a great deal of attention as an attractive synthetic target due to its intriguing molecular architecture and significant immunosuppressive activity, and we achieved its total synthesis in 2015. However, the synthesized palau''amine has not been readily applicable to the mechanistic study of immunosuppressive activity, because it requires 45 longest linear steps from a commercially available compound. Here, we report the short-step construction of the ABCDEF hexacyclic ring core of palau''amine. The construction of the CDE tricyclic ring core in a single step is achieved by our pK_a concept for proceeding with unfavorable equilibrium reactions, and a palau''amine analog without the aminomethyl and chloride groups is synthesized in 20 longest linear steps from the same starting material. The palau''amine analog is confirmed to retain the immunosuppressive activity. The present synthetic approach for a palau''amine analog has the potential for use in the development of palau''amine probes for mechanistic elucidation.

A palau''amine analog (2) was synthesized from 2-cyclopentenone in 20 steps. The construction of the CDE tricyclic ring core in a single step is achieved by our pK_a concept for proceeding with the unfavorable equilibrium reactions.     

Safety Evaluation of Far-UV-C Irradiation to Epithelial Basal Cells in the Corneal Limbus

Basal cells in the corneal limbus play an important role in the turnover cycle because they are the source of all cells that constitute the corneal epithelium. We examined the penetration depth of ultraviolet (UV) light in the corneal limbus and assessed the safety of Far-UV-C on stem cells in the basal area of the corneal limbus. Rats were irradiated with UV at peaks of 207, 222, 235, 254 and 311 nm while under anesthesia. The UV penetration depth in the rat corneal limbal epithelium was wavelength dependent: 311 nm UV-B and 254 nm UV-C reached the basal cells of the epithelium, and 235 nm radiation reached the middle area; however, 207 and 222 nm UV-C reached only the superficial layer of the epithelium. Porcine cornea, which is similar to the human eye in size and structure, were irradiated with 222 and 254 nm UV-C. As in rats, 222 nm UV-C reached only the superficial layer of the porcine corneal limbal epithelium. These results indicate that Far-UV-C, such as radiation of wavelengths of 207 and 222 nm, could not reach corneal epithelial stem cells, i.e. the cells remained intact. It is unlikely that the turnover of the corneal epithelium is obstructed or disrupted by exposure to Far-UV-C.     

On a synchronization queue with two finite buffers

In this paper, we consider a synchronization queue (or synchronization node) consisting of two buffers with finite capacities. One stream of tokens arriving at the system forms a Poisson process and the other forms a PH-renewal process. The tokens are held in the buffers until one is available from each flow, and then a group-token is instantaneously released as a synchronized departure. We show that the output stream of a synchronization queue is a Markov renewal process, and that the time between consecutive departures has a phase type distribution. Thus, we obtain the throughput of this synchronization queue and the loss probabilities of each type of tokens. Moreover, we consider an extended synchronization model with two Poisson streams where a departing group-token consists of several tokens in each buffer. This revised version was published online in June 2006 with corrections to the Cover Date.     

Inelastic stress-responses of an aluminium alloy in non-proportional deformations at elevated temperature

Some characteristics of strain-induced anisotropy and effects of strain-rate on them are experimentally investigated under non-proportional loadings at elevated temperature. By applying combined loadings of axial force and internal pressure to thin-walled tubes of an aluminium alloy at 200°C, inelastic stress-responses are observed at several constant strain-rates along bilinear strain trajectories. It is found that a softening of material and a non-coaxiality between stress and inelastic strain-increment deviators occur after the corner of bilinear strain trajectory. These phenomena appear more markedly and then decay more gradually with the increase of corner angle and/or strain-rate. Experimental results are qualitatively discussed in terms of the activation of piled-up dislocations as well as the so-called back stress and drag stress.     

Rotational spectrum of the Ar–dimethyl sulfide complex

The rotational spectra of three isotopomers of the Ar–dimethyl sulfide (DMS) complex – normal, ³⁴S, and ¹³C species – were measured in the frequency region from 3.7 up to 24.1 GHz by Fourier transform microwave spectroscopy. The normal species yielded 43 a-type and 79 c-type transitions. No Ar tunneling splitting was observed, while many transitions were split by the internal rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to that due to methyl internal-rotation, several forbidden transitions were observed that followed b-type selection rules. All of the observed transition frequencies were analyzed simultaneously using a phenomenological Hamiltonian also used in previously published work describing the Ar–dimethyl ether (DME) and Ne–DME complexes. The rotational and centrifugal distortion constants and the potential barrier height to methyl-top internal rotation, V₃, were determined. The rotational constants were consistent with an Ar–DMS center of mass (cm) distance of 3.796 (3) Å and a S–cm–Ar angle of 104.8 (2)°. The V₃ potential barrier obtained, 736.17 (32) cm⁻¹, was 97.8% of the DMS monomer barrier. By assuming a Lennard–Jones-type potential, the dissociation energy was estimated to be 2.4 kJ mol⁻¹, which was close to the value for Ar–DME, 2.5 kJ mol⁻¹.     

Heat transfer in lattice BGK modeled fluid

The thermal lattice BGK model is a recently suggested numerical tool aiming at solving problems of thermohydrodynamics. The quality of the lattice BGK simulation is checked in this paper by calculating temperature profiles in the Couette flow under different Eckert and Mach numbers. A revised lower order model is proposed to improve the accuracy and the higher order model is proved to be advantageous in this respect, especially in the flow regime with a higher Mach number.     

Oxidation activity of Au nanoparticles on aerogel supports

We have prepared titania aerogel and titania-coated silica aerogel incorporating thiol-capped Au nanoparticles. Both composite materials showed high CO oxidation activity after they were calcined at 673 K. Compositional and morphological changes driven by calcination were evaluated with thermogravimetry and X-ray diffractometry. From the results, it was suggested that the nanoparticles transformed from a faulted to a near-regular FCC structure presumably in concert with the formation of firm contacts between the nanoparticles and the gel substrates. While the diameters of the Au particles in the titania aerogel considerably increased upon calcination, those in the titania-coated silica aerogel were almost unchanged. As a consequence, the latter composite aerogel showed higher activity for oxidation of CO.