Further studies on palytoxin. II. structure of palytoxin

The full structure of palytoxin, a potent coelenterate toxin, is reported.     

DNA damage by fasicularin

Fasicularin is a structurally novel thiocyanate-containing alkaloid isolated from the ascidian Nephteis fasicularis. Early biological experiments suggested that this compound's cytotoxic properties may stem from its ability to damage cellular DNA. Sequence gel analysis reveals that treatment of a 5'-32P-labeled DNA duplex with fasicularin in pH 7.0 buffer causes strand cleavage selectively at guanine residues. Further experiments indicate that production of these base-labile lesions in DNA involves alkylation of guanine residues by a fasicularin-derived aziridinium ion. This work reveals fasicularin as the first natural product found to generate a DNA-alkylating aziridinium ion via a mechanism analogous to the clinically used anticancer drugs mechlorethamine, melphalan, and chlorambucil.     

Stereoselective cross-coupling reaction of 1,1-Diboryl-1-alkenes with electrophiles: a highly stereocontrolled approach to 1,1,2-triaryl-1-alkenes

Palladium-catalyzed cross-coupling reaction of 1,1-diboryl-1-alkenes with aryl and alkenyl iodides was found to proceed stereoselectively, giving rise to the corresponding mono-coupled product as a single diastereomer with E-configuration. Second coupling of the initial product with another aryl iodide affords diverse triarylalkenes in their stereochemically pure form. This highly stereoselective approach for triarylalkenes allows one to synthesize both diastereomers in one pot from 1,1-diboryl-1-alkenes.     

Efficient asymmetric synthesis of α-amino acids through hydrogenation of α,β-dehydroamino acid residue in cyclic dipeptides

A series of cyclo (Δaminoacyl-L-Ala) ($\text{4}$) (Δ=α,β-dehydro) were prepared from cyclo(Gly-L-Ala) and corresponding aldehyde, and hydrogenated with Pd black in MeOH. Chiral inductions producing cyclo (L-aminoacyl-L-Ala) ($\text{5}$) from $\text{4}$ were 96–99% in the case of L-Aba (2-aminobutanoic acid), L-Val, L-Leu, and L-App (2-amino-5-phenylpentanoic acid) as an L-aminoacyl moiety in $\text{5}$. Pure L-Leu, L-Aba, and L-App were synthesized in preparative scale from corresponding $\text{4}$ through asymmetric hydrogenation and acid-hydrolysis.     

Improvements in Carrier-to-Noise-Ratio (CNR) of Lightwave Amplitude Modulated Vestigial-Sideband (AM-VSB) Transmission Systems by the Use of Optical Isolators

In lightwave community antena television (CATV) systems as well as other optical fiber communication networks, a transmitted optical signal is known to be degraded by an intensity noise produced within the fiber due to the interference between the signal and doubly reflected light. We report on the improvements to the signal degradation due to the double Rayleigh backscattering by inserting optical isolators in the trunk lines of the systems. A carrier-to-noise ratio (CNR) has been calculated as a function of the number and the insertion loss of the isolators. The calculated results indicate that there is an optimum number of isolators, and if the insertion loss is less than 0.3 dB, the CNR degradation can be restored by more than 60%. To test the calculated results, we conducted experiments for the specific case of employing one isolator, and obtained good agreements between the two.     

Intravoxel incoherent motion imaging of the kidney: alterations in diffusion and perfusion in patients with renal dysfunction

Purpose

To investigate the relationship between estimated glomerular filtration rate (eGFR) and parameters calculated using intravoxel incoherent motion (IVIM) imaging of the kidneys.

Materials and Methods

We studied 365 patients, divided into 4 groups based on eGFR levels (mL/min/1.73 m²): group 1, eGFR ≥ 80(n = 80); group 2, eGFR 60–80 (n = 156); group 3, eGFR 30–60 (n = 114); and group 4 ,eGFR < 30 (n = 15). IVIM imaging was used to acquire diffusion-weighted images at 12 b values. The diffusion coefficient of pure molecular diffusion (D), the diffusion coefficient of microcirculation or perfusion (D*), and perfusion fraction (f) were compared among the groups using group 1 as control.

Results

In the renal cortex, D* values were significantly lower in groups 2, 3, and 4 than in group 1. The D value of renal cortex was significantly low in only group 3. In the renal medulla, the D* and D values were significantly lower only in groups 2 and 3, respectively.

Conclusion

As renal dysfunction progresses, renal perfusion might be reduced earlier and affected more than molecular diffusion in the renal cortex. These changes are effectively detected by IVIM MR imaging.     

TOF-SIMS structural characterization of self-assembly monolayer of cytochrome b5 onto gold substrate

Orientation and three-dimensional structure of immobilized proteins on bio-devices are very important to assure their high performance. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is able to analyze upper surface of one layer of molecules. Orientation of immobilized proteins can be evaluated based on determination of a partial structure, representing ensemble of amino acids, on the surface part. In this study, a monolayer of cytochrome b5 was reconstituted onto gold substrate and investigated by surface plasmon resonance (SPR). After freeze-drying, the resulted protein self-assembly was evaluated using TOF-SIMS with the bismuth cluster ion source, and then TOF-SIMS spectra were analyzed to select peaks specific to cytochrome b5 and identify their chemical formula and ensembles of amino acids. The results from TOF-SIMS spectra analysis were compared to the amino acid sequence of the modified cytochrome b5 and three-dimensional structure of cytochrome b5 registered in the protein data bank. Finally, fragment-ion-generating parts of the immobilized-cytochrome b5 are determined based on the suggested residues and three-dimensional structure. These results suggest the actual structure and confirm the expected orientation of immobilized protein.     

TOF-SIMS analysis of magnetic materials in chum salmon head

A piece of tissue extracted from a chum salmon Oncorhynchus keta head was measured with time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to evaluate the distribution and composition of magnetic materials in the tissue, which may concern with geomagnetic navigation of long-distance migrating salmon. Several depositions of iron compounds were detected in the tissue by TOF-SIMS analysis. Comparing with total ion images providing a topological tissue structure, specific distribution of iron ion in the tissue was clearly shown. Higher magnification TOF-SIMS analysis revealed the existence of the aggregations of iron particles. Iron oxide clusters comprising many submicron particles were also detected in the tissue using scanning electron microscopy and X-ray analysis, suggesting the common existence of submicron-scale iron oxides in salmon heads. These results suggest that TOF-SIMS analysis is a valid method to clarify detailed structures and chemical properties of candidate magnetoreceptors in fish heads.