A new, highly sensitive time-of-flight mass spectrometer consisting of a flangeon-type conical ion lens system and a proto-type Daly detector for exhaust gas analysis based on the Jet-REMPI technique.

For the analysis of trace amounts of hazardous organic compounds, we developed a new ion detection system for supersonic jet resonance-enhanced multiphoton laser ionization mass spectrometry. High sensitivity and selectivity have been achieved by combining a proto-type Daly detector, a newly designed conical ion lens, and a potential switch that can perform the function of a mass selector. This ion detection system enables us to bring the jet nozzle closer to the ionization point. The detection sensitivity has thus been improved totally by more than 100 times compared with that obtained by the parallel-plate electrodes and micro-channel plate. We succeeded in assembling a flangeon-type ion extraction electrode consisting of a conical ion lens and a potential switch.     

Alkali and Alkaline Earth Metal Ions Complexes with a Partial Peptide of the Selectivity Filter in K+ Channels Studied by a Cold Ion Trap Infrared Spectroscopy

The infrared (IR) spectra of alkali and alkaline earth metal ion complexes with the Ac-Tyr-NHMe (GYG) peptide have been measured by laser photodissociation in a cold ion trap coupled with an electrospray mass spectrometer. The GYG peptide corresponds to a portion of the ion selectivity filter in the KcsA K⁺ channel that allows K⁺ to pass, but blocks Na⁺ even though it has a smaller ionic radius than K⁺. This current study extends a previous investigation on Na⁺ and K⁺ to the entire set of alkali metaI ions and alkaline earth dications. IR-IR hole-burning (IR² dip) spectroscopy has established the coexistence of several conformers of the GYG-metal ion complexes. The structures of the conformers were assigned by comparison between the isomer-selected IR spectra and theoretical IR spectra obtained from quantum chemical calculations. It was found that the structure of the dominant conformer correlates with the ability of the ion to permeate through the K⁺ channel.     

Structure elucidation of EI-1941-1 and -2, novel interleukin-1β converting enzyme inhibitors produced by Farrowia sp. E-1941

EI-1941-1 (1a) and EI-1941-2 (2a) accompanied by EI-1941-3 (3) have been isolated from culture broth of Farrowia sp. E-1941 as the inhibitors of interleukin-1β converting enzyme. The structures of 1a, 2a, and 3 were elucidated by the analysis of NMR and MS data, and finally the absolute stereochemistries of 1a and 2a were confirmed by optical rotation data, or X-ray crystallographic analysis of p-bromobenzoate, 2b, respectively.     

Enzymatic synthesis of chondroitin and its derivatives catalyzed by hyaluronidase

The enzymatic polymerization to provide synthetic chondroitin and its derivatives is reported here, the first example of such in vitro synthesis to date. N-Acetylchondrosine (GlcAbeta(1-->3)GalNAc) oxazoline (1a) and its derivatives (1b-1f) were designed and synthesized as novel transition state analogue substrate monomers for catalysis by hyaluronidase. Hyaluronidase is a hydrolysis enzyme of chondroitin that also catalyzes the formation of repeated glycosidic bonds in in vitro synthesis, rather than in the catabolic direction. Monomers of 2-methyl (1a), 2-ethyl (1b), and 2-vinyl (1f) oxazoline derivatives were polymerized using this enzyme, via ring-opening polyaddition with total control of regioselectivity and stereochemistry. These reactions provided the corresponding synthetic chondroitin (natural type; N-acetyl, 2a) and the derivatives (unnatural type) with N-propionyl (2b) and N-acryloyl (2f) functional groups at the C2 position of all the galactosamine units, in good yields. Monomers of 2-n-propyl (1c) and 2-isopropyl (1d) oxazoline derivatives were polymerized to produce 2c and 2d in low yield. The 2-phenyl oxazoline derivative (1e) did not afford any enzyme-catalyzed products. M(n) values of 2a and 2b reached 4800 and 4000, respectively. The M(n) value of 2a corresponds to that of the naturally occurring chondroitin. Thus, hyaluronidase catalysis allows the in vitro production of not only natural type but also the formation of unnatural type chondroitins.     

Three new types of indoloditerpenes, emindole PA-PC, from Emericella purpurea. Revision of the structure of emindole PA

Three new type indoloditerpenes, emindoles PA (1), PB (2), and PC (3), were isolated from the mycelium of Emericella purpurea along with the sesterterpenes variecolol and variecolactone, and the dicyanide derivatives epurpurins A to C. The structures of 1-3 were confirmed by the spectroscopic investigation. The structure of emindoles PA (1) was revised from our preliminary report. Emindoles PA (1), PB (2), and PC (3) are the indoloditerpenes having a new type of carbon skeleton.     

Ionization-induced π→ H site switching dynamics in phenol-Ar3

Electronic excitation spectra of the S(1)← S(0) transition obtained by resonance-enhanced two-photon ionization (REMPI) are analysed for phenol-Ar(n) (PhOH-Ar(n)) clusters with n≤ 4. An additivity rule has been established for the S(1) origin shifts upon sequential complexation at various π binding sites, which has allowed for the identification of two less stable isomers not recognized previously, namely the (2/0) isomer for n = 2 and the (2/1) isomer for n = 3. Infrared (IR) spectra of neutral PhOH-Ar(n) and cationic PhOH(+)-Ar(n) clusters are recorded in the vicinity of the OH and CH stretch fundamentals (ν(OH), ν(CH)) in their S(0) and D(0) ground electronic states using IR ion dip spectroscopy. The small monotonic spectral redshifts Δν(OH) of about -1 cm(-1) per Ar atom observed for neutral PhOH-Ar(n) are consistent with π-bonded ligands. In contrast, the IR spectra of the PhOH(+)-Ar(n) cations generated by resonant photoionization of the neutral precursor display the signature of H-bonded isomers, suggesting that ionization triggers an isomerization reaction, in which one of the π-bonded Ar ligands moves to the more attractive OH site. The dynamics of this isomerization reaction is probed for PhOH(+)-Ar(3) by picosecond time-resolved IR spectroscopy. Ionization of the (3/0) isomer of PhOH(+)-Ar(3)(3π) with three π-bonded Ar ligands on the same side of the aromatic ring induces a π→ H switching reaction toward the PhOH(+)-Ar(3)(H/2π) isomer with a time constant faster than 3 ps. Fast intracluster vibrational energy redistribution prevents any H →π back reaction.     

Photoionization-induced large-amplitude pendular motion in phenol(+)-Kr

The dynamics of the intermolecular motion of the phenol(+)-Kr cation generated by photoionization of the neutral π-structure is probed by picosecond time-resolved infrared spectroscopy. The spectrum at zero delay displays only the free OH stretch band of the π-structure. The appearance of the hydrogen-bonded OH stretch band of the H-structure after a few ps is due to ionization-induced π → H site switching. Spectra at long delay (>20 ns) show that the Kr atom delocalizes from one π-site of the aromatic ring to the opposite π-site via the OH-site, like a pendular motion in the classical picture.