First enantioselective synthesis of salinipostin A,a marine cyclic enol-phosphotriester isolated from Salinispora sp

Salinipostins are cyclic enol-phosphotriesters isolated from a marine-derived Salinispora sp. as antimalarial compounds. Herein, the first enantioselective synthesis of salinipostin A was achieved. Organocatalyst-mediated asymmetric cyclopropanation and regioselective cyclopropane ring opening were the key steps.     

Practical and Scalable Organic Reactions with Flow Microwave Apparatus

Microwave irradiation has been used for accelerating organic reactions as a heating method and has been proven to be useful in laboratory scale organic synthesis. The major drawback of microwave chemistry is the difficulty in scaling up, mainly because of the low penetration depth of microwaves. The combination of microwave chemistry and flow chemistry is considered to overcome the problem in scaling up of microwave‐assisted organic reactions, and some flow microwave systems have been developed in both academic and industrial communities. In this context, we have demonstrated the scale‐up of fundamental organic reactions using a novel flow microwave system developed by the academic‐industrial alliance between the University of Shizuoka, Advanced Industrial Science and Technology, and SAIDA FDS. In this Personal Account, we summarize the recent progress of our scalable microwave‐assisted continuous synthesis using the SAIDA flow microwave apparatus.     

Adaptive echolocation sounds of insectivorous bats, Pipistrellus abramus, during foraging flights in the field

Echolocation pulses emitted by wild Pipistrellus abramus were investigated while foraging for insects in the field. Similar to other European pipistrelles, the frequency structure during foraging varied. During the search phase, the bats emitted long shallow frequency-modulated pulses 9-11 ms in duration, whereas the maximum pulse duration of the bats approaching a large target wall in the laboratory was 3 ms. No significant difference was observed between decreases in the interpulse interval during these two approach flights. It is concluded that the bats use a long quasi-constant frequency pulse to find a weak echo from a small prey target.     

Effective Application of Microwave Resonant Cavity System to Flow Chemistry

By applying advanced telecommunication solid state devices to microwave (MW) resonant cavity system for flow chemistry, it becomes possible to heat up low polarity solvents higher than 250 C, that are considered impossible to heat up by MW until now. The resonant cavity system is opening new process windows to production processes of specialty chemicals which require low cost, high yield and high productivity.     

How Self-Assembled Nanodomains Can Impact the Organization of a Phospholipid Monolayer-Flower-Like Arrays

We found that monolayers of dipalmitoylphosphatidylcholine (DPPC) and semi-fluorinated tetrablock di(F10H16) self-assemble to form a new type of large, complex flower-like patterns on the surface of water and on solid substrates. The hierarchical organization of these unusual self-assemblies was investigated using compression and surface potential isotherms, in situ fluorescence and Brewster angle microscopies, and atomic force microscopy after transfer.     

Optical,structural, enhanced local vibrational and fluorescence properties in K-doped ZnO nanostructures

We studied structural, optical and vibrational properties of K-doped ZnO nanostructures. X-ray diffraction studies reveal that the prepared particles are hexagonal wurtzite in structure. Increase in lattice parameters and unit cell volume is observed after K doping. Dopant influences on stress, strain of the system are studied using W–H plots. Band gap variation by doping of K is identified from optical absorption studies. Photoluminescence studies have given insight into the enhancement in blue emission observed by K doping along with the near band emission of nano ZnO. From Fourier transform infrared spectral measurements, K-related local vibration mode is observed along with the information related to influence of doping on characteristic vibrational modes of ZnO.     

Concise total synthesis of (-)-spongotine A

The first asymmetric total synthesis of spongotine A is described. The oxidative synthesis of the imidazoline/ketone unit from keto aldehyde and diamine is a key step in this synthesis. The absolute stereochemistry of the asymmetric center of natural spongotine A is revealed as the (S)-configuration.     

Solution properties of perfluorinated anionic surfactants with divalent counterion of separate electric charges

Novel surfactants of perfluorinated double long-chain salts with divalent counterion of separate electric charge, 1,1-(1,omega-alkanediyl)bispyridinium diperfluorononanoate (CnBP(FC9)2, n = 2, 4, 6, 8) were newly synthesized. Their solution properties were investigated by surface tension measurement over the temperature range from 298.2 to 313.2 K, where magnesium diperfluorononanoate (Mg(FC9)2) was employed as a reference surfactant with divalent counterion of concentrated electric charge. From change of surface tension with concentration, the critical micelle concentration (CMC), surface excess (Gamma), apparent molecular surface area (A), and -log(concentration to reduce surface tension of water by 20 mN m-1) (pC20) were determined. The CMC values of CnBP(FC9)2 decreased with increasing charge separation and with increasing temperature, where the values of CnBP(FC9)2 were much smaller than those of Mg(FC9)2. In addition, the pC20 values of the former were also much larger than those of the latter. These results indicate a strong influence of the extent of charge separation or the spacer length of the counterions upon surface activity of the fluorinated surfactants. The surface excess or the corresponding apparent molecular surface area monotonously changed with the spacer length (n < or = 6), whereas the behavior for n = 8 was much different from the other CnBP(FC9)2 due to conformational change in the in-between alkanediyl chain. The entropy changes (Deltas) for the surface adsorption or condensation were found to be mostly negative for CnBP(FC9)2, where the changes approached zero with an increase in the charge separation. On the other hand, the changes for Mg(FC9)2 were positive over the whole concentration below the CMC. In addition, Brewster angle microscopy indicated no condensation of the present surfactants just at the air/solution interface.     

High-field 1H MAS and 15N CP-MAS NMR studies of alanine tripeptides and oligomers: distinction of antiparallel and parallel beta-sheet structures and two crystallographically independent molecules

beta-Strand peptides are known to assemble into either antiparallel (AP) or parallel (P) beta-sheet forms which are very important motifs for protein folding and fibril formations occurring in silk fibroin or amyloid proteins. Well-resolved 1H NMR signals including NH protons were observed for alanine tripeptides (Ala)3 with the AP and P structures as well as (Ala)n (n = 4-6) by high-field/fast magic-angle spinning NMR. Amide NH and amino NH3+ 1H signals of (Ala)3 with the P structure were well resonated at 7.5 and 8.9 ppm, respectively, whereas they were not resolved for the AP structure. Notably, NH 1H signals of (Ala)3 and (Ala)4 taking the P structure are resonated at higher field than those of the AP structure by 1.0 and 1.1 ppm, respectively. Further, NH 15N signals of (Ala)3 with the AP structure were resonated at lower field by 2 to 5 ppm than those of (Ala)3 with the P structure. These relative 1H and 15N hydrogen bond shifts of the P structure with respect to those of the AP structure are consistent with the relative hydrogen bond lengths of the interstrand N-H...O=C bonds. Distinction between the two crystallographically independent chains present in the AP and P structures was feasible by 15N chemical shifts but not by 1H chemical shifts because of insufficient spectral resolution in the latter. Calculated 1H and 15N shielding constants by density functional theory are generally consistent with the experimental data, although some discrepancies remain depending upon the models used.