The odor of a nontoxic tetrodotoxin analog, 5,6,11-trideoxytetrodotoxin, is detected by specific olfactory sensory neurons of the green spotted puffers.

Toxic puffers accumulate tetrodotoxin (TTX), a well-known neurotoxin, by feeding on TTX-bearing organisms and using it to defend themselves from predators. Our previous studies have demonstrated that toxic puffers are attracted to 5,6,11-trideoxytetrodotoxin (TDT), a nontoxic TTX analog that is simultaneously accumulated with TTX in toxic puffers and their prey. In addition, activity labeling using immunohistochemistry targeting neuronal activity marker suggests that TDT activates crypt olfactory sensory neurons (OSN) of the green spotted puffer. However, it remains to be determined whether individual crypt OSNs can physiologically respond to TDT. By employing electroporation to express GCaMP6s in OSNs, we successfully identified a distinct group of oval OSNs that exhibited a specific calcium response when exposed to TDT in green spotted puffers. These oval OSNs showed no response to amino acids (AAs), which serve as food odor cues for teleosts. Furthermore, oval morphology and surface positioning of TDT-sensitive OSNs in the olfactory epithelium closely resemble that of crypt OSNs. These findings further substantiate that TDT is specifically detected by crypt OSNs in green spotted puffer. The TDT odor may act as a chemoattractant for finding conspecific toxic puffers and for feeding TTX-bearing organisms for effective toxification.

Tacticity Characterization of Biosynthesized Polyhydroxyalkanoates Containing (S)- and (R)-3-Hydroxy-2-Methylpropionate Units.

Polyhydroxyalkanoates (PHAs), aliphatic polyesters synthesized by microorganisms, have gained considerable attention as biodegradable plastics. Recently, α-carbon-methylated PHAs have been shown to exhibit several interesting properties that differ from those of conventional PHAs, such as their crystallization behavior and material properties. This study investigated α-carbon methylated (S)- and (R)-3-hydroxy-2-methylpropionate (3H2MP) as new repeating units. 3H2MP units were homopolymerized or copolymerized with (R)-3-hydroxybutyrate (3HB) by manipulating the culture conditions of recombinant Escherichia coli LSBJ. Consequently, PHAs with 3H2MP units ranging from 5 to 100 mol % were synthesized by external addition of (R)- and (S)-enantiomers or the racemic form of 3H2MPNa. The (S)-3H2MP precursor supplemented into the culture medium was almost directly polymerized into PHA while maintaining its chirality. Therefore, a highly isotactic P(3H2MP) (R:S = 1:99) was synthesized, which displayed a melting temperature of 114-119 °C and a relatively high enthalpy of fusion (68 J/g). In contrast, in cultures supplemented with (R)-3H2MP, the precursor was racemized and polymerized into PHA, resulting in the synthesis of the amorphous polymer atactic P(3H2MP) (R:S = 40:60). However, racemization was not observed at a low concentration of the (R)-3H2MP precursor, thereby synthesizing P(3HB-co-8 mol % 3H2MP) with 100% (R)-3H2MP units. The thermogravimetric analysis revealed that the thermal degradation temperatures at 5% weight loss of P(3H2MP)s occurred at approximately 313 °C, independent of tacticity, which is substantially higher than that of P(3HB) (257 °C). This study demonstrates a new concept for controlling the physical properties of biosynthesized PHA by manipulating the polymers' tacticity using 3H2MP units.

Phase textures of metal-oxide nanocomposites self-orchestrated by atomic diffusions through precursor alloys.

Metal-oxide nanocomposites (MONs) are of pivotal importance as electrode materials, yet lack a guiding principle to tune their phase texture. Here we report that the phase texture of MONs can be tuned at the nanoscale by controlling the nanophase separation of precursor alloys. In situ transmission electron microscopy (in situ TEM) has demonstrated that a MON material of platinum (Pt) and cerium oxide (CeO2) is obtained through promoted nanophase separation of a Pt5Ce precursor alloy in an atmosphere containing oxygen (O2) and carbon monoxide (CO). The Pt-CeO2 MON material comprised an alternating stack of nanometre-thick layers of Pt and CeO2 in different phase textures ranging from lamellae to mazes, depending on the O2 fraction in the atmosphere. Mathematical simulations have demonstrated that the phase texture of MONs originates from a balance in the atomic diffusions across the alloy precursor, which is controllable by the O2 fraction, temperature, and composition of the precursor alloys.

Synthesis and Characterization of the Orthorhombic Sn3 O4 Polymorph.

An unexplored tin oxide crystal phase (Sn3 O4 ) was experimentally synthesized via a facile hydrothermal method. After tuning the often-neglected parameters for the hydrothermal synthesis, namely the degree of filling of the precursor solution and the gas composition in the reactor head space, an unreported X-ray diffraction pattern was discovered. Through various characterization studies, such as Rietveld analysis, energy dispersive X-ray spectroscopy, and first-principles calculations, this novel material was characterized as orthorhombic mixed-valence tin oxide with the composition SnII 2 SnIV O4 . This orthorhombic tin oxide is a new polymorph of Sn3 O4 , which differs from the reported conventional monoclinic structure. Computational and experimental analyses showed that orthorhombic Sn3 O4 has a smaller band gap (2.0 eV), enabling greater absorption of visible light. This study is expected to improve the accuracy of hydrothermal synthesis and aid the discovery of new oxide materials.

Green spotted puffers detect a nontoxic TTX analog odor using crypt olfactory sensory neurons.

Toxic puffers accumulate their defense substance (tetrodotoxin; TTX) through the food chain. Although the previous study suggests that 5,6,11-trideoxyTTX, a nontoxic TTX analog detected simultaneously with TTX in toxic puffers or their prey, acts as an olfactory chemoattractant for grass puffers, it is unclear whether toxic puffers are commonly attracted to 5,6,11-trideoxyTTX, and which types of olfactory sensory neurons (OSNs) detect 5,6,11-trideoxyTTX. Here, we demonstrated that green spotted puffer, a phylogenetically distant species from the grass puffer, is attracted to 5,6,11-trideoxyTTX. 5,6,11-TrideoxyTTX administration made green spotted puffers stay longer at the administered site, whereas a food odor (l-Arg) made them actively swim throughout the aquarium. Attractive responses were not observed when TTX or its vehicle was administered, nor when 5,6,11-trideoxyTTX was administered to anosmic fish. Furthermore, double immunohistochemistry with activity marker and crypt OSN marker antibodies labeled oval cells with apical invagination on the olfactory epithelium surface treated with 5,6,11-trideoxyTTX. These results suggest that 5,6,11-trideoxyTTX acts as an olfactory chemoattractant detected by crypt OSNs, and attraction to 5,6,11-trideoxyTTX odor appears to be a trait shared by toxic puffers for social communication or effective toxification.

Bandgap widening through doping for improving the photocatalytic oxidation ability of narrow-bandgap semiconductors.

The trade-off relationship between narrowing the bandgap and achieving sufficient redox potentials accounts for the hindrance to the development of an efficient photocatalyst. Most of the previous researchers attempt to narrow the bandgap of semiconductors by impurity doping to achieve visible-light sensitivity, but this approach causes the losses of their oxidation and/or reduction ability. Conversely, this study presents a bandgap widening strategy by doping to improve the redox potential of photogenerated carriers. Employing first-principles simulations, we propose the lanthanum-doped bismuth vanadate (La-BiVO4) photocatalyst as a wider-bandgap semiconductor exhibiting stronger oxidation ability compared to pristine BiVO4, and the results revealed that the bismuth orbital in the valence band (VB) was diluted by lanthanum-ion doping, while the VB shifted to a higher potential (positively shifted). Thereafter, a La-BiVO4 powder was synthesized via a solid-state reaction, after which its activity was evaluated in the photocatalytic oxidation of 2-propanol (IPA). La-BiVO4 exhibited bandgap widening; thus, the number of absorbed photons under visible-light irradiation was lower than that of pristine BiVO4. However, the quantum efficiency (QE) of La-BiVO4 for the oxidation of IPA was higher than that of the pristine BiVO4. Consequently, the photocatalytic reaction rate of La-BiVO4 was superior to that of pristine BiVO4 under the same visible-light irradiation conditions. Although the bandgap of La-BiVO4 is widened, it is still sensitive to the cyan-light region, which is the strongest in the sunlight spectrum. These results demonstrate that the orbital dilution strategy by impurity elemental doping is effective for bandgap widening and contributes to improving the oxidation and/or reduction ability of the photogenerated charge carriers. This study elucidates the possibility of boosting photocatalytic performances via bandgap widening.

In vitro thrombus formation and in vivo hemostasis mediated by platelets irradiated with bactericidal ultraviolet C from xenon flash under flow conditions.

BACKGROUND: We previously reported a flow path-ultraviolet C (UVC) irradiation system for platelet concentrates (PCs) with platelet additive solution (PAS) to minimize contamination by bacteria. Here, we investigated functionalities of irradiated platelets (PLTs) in in vitro thrombus formation and in vivo hemostasis. STUDY DESIGN AND METHODS: PAS-PCs were irradiated with flash UVC using the flow path system. Their variables (PLT count, mean platelet volume, pH, glucose, lactate, glycoprotein [GP] Ib, and activated integrin αIIbß3) were evaluated. Static adhesion to collagen or fibrinogen was analyzed using fluorescent microscopy. Thrombus formation under flow conditions was assessed using a collagen-coated bead column. Adenosine diphosphate (ADP)-induced Akt phosphorylation was determined by western blot. In vivo hemostasis and circulatory survival of PLTs were assessed with a rabbit bleeding model. RESULTS: All variables, except for GPIb expression, were slightly, but significantly, impaired after flash UVC irradiation throughout the 6-day storage period. No difference was observed in static adhesion to either collagen or fibrinogen between irradiated and nonirradiated PAS-PCs. In vitro thrombus formation of flash UVC-irradiated PAS-PCs was significantly greater than that of nonirradiated PAS-PCs. ADP-induced Akt phosphorylation was enhanced in irradiated PAS-PCs. In vivo hemostatic efficacy was comparable between the groups on Day 1. The efficacy declined in nonirradiated PAS-PCs on Day 5, while it was retained in flash UVC-irradiated PAS-PCs. Circulatory survival of PLTs was lower in irradiated PAS-PCs. CONCLUSIONS: PAS-PCs irradiated with UVC from xenon flash have favorable properties to achieve hemostasis compared with nonirradiated PAS-PCs.

Flow path system of ultraviolet C irradiation from xenon flash to reduce bacteria survival in platelet products containing a platelet additive solution.

BACKGROUND: Our previous study showed that ultraviolet C (UVC) from xenon (Xe) flash without any photoreactive compounds inactivated bacteria in platelet concentrates (PCs) with less damage to platelets (PLTs) as compared with Xe flash containing ultraviolet A, ultraviolet B, and visible light. Here, we report a UVC irradiation system for PCs under flow conditions consisting of a flow path-irradiation sheet, a peristaltic pump, and a collection bag. STUDY DESIGN AND METHODS: Platelet concentrates containing Ringer's solution (R-PCs) inoculated with bacteria were injected into a flow path sheet using a peristaltic pump, being irradiated with UVC from Xe flash. The quality of the irradiated PCs containing platelet additive solution (PAS-PCs) was assessed based on PC variables, PLT surface markers, and aggregation ability. RESULTS: Streptococcus dysgalactiae (12 tests) and Escherichia coli (11) were all negative on bacterial culture, while Staphylococcus aureus (12) and Klebsiella pneumoniae (14) grew in one and two R-PCs, respectively. Bacillus cereus spores were inactivated in 7 of 12 R-PCs. PC variables became significantly different between irradiated and nonirradiated PAS-PCs. P-selectin, first procaspase-activating compound (PAC-1) binding, and phosphatidylserine increased by irradiation. Aggregability stimulated by adenosine diphosphate, collagen, or thromboxane A2 increased in the irradiated PAS-PCs, while that by thrombin became smaller compared with nonirradiated controls. CONCLUSION: This newly developed system inactivated bacteria including spores in R-PCs. PAS-PCs irradiated by this system retained acceptable in vitro quality and aggregability. Usage of a peristaltic pump instead of agitator during irradiation may enable this system to be directly combined with an apheresis blood cell separator.

Correlation between platelet thrombus formation on collagen-coated beads and platelet aggregation induced by ADP.

BACKGROUND: The thrombus-forming ability is a critical in vitro parameter to assess platelets (PLTs), but flow-based methods using collagen-coated materials generally require multistep, proficiency, and advanced analysis. STUDY DESIGN AND METHODS: Commercially available collagen-coated bead columns were examined to assess thrombus-forming ability of PLTs. The retention rate as an index of thrombus formation was calculated using the PLT count before and after column passage. Thrombi were imaged by anti-CD41 using a fluorescent microscope. PLT aggregation was measured by light-transmitting aggregometry. RESULTS: The retention rate was low when apheresis-collected PLT concentrates (PCs) were suspended in plasma either with or without Ca2+. Reconstitution of PCs with red blood cells (RBCs) increased the retention rate with good reproducibility on repeated-measurements, and therefore, PLT samples were reconstructed with RBCs in subsequent experiments. The retention rate of PCs varied widely in a product-dependent manner, and was correlated with the aggregation rate induced by ADP, but not that by collagen. Using platelet-rich-plasma, antagonists of P2Y1 or P2Y12 receptors for ADP reduced both the retention and aggregation of PLTs. Acetylsalicylic acid reduced retention, although it had no effect on ADP-induced aggregation. Prostaglandin E1 significantly inhibited both retention and aggregation. These anti-PLT reagents resulted in reduced or no thrombus formation on the beads. CONCLUSION: The collagen-coated bead column was useful to readily examine the thrombus-forming ability of PLTs. Variance of the PLT retention rate was correlated with responsiveness to ADP. Results from anti-PLT reagents revealed that thrombus formation on collagen-coated beads was similar to in vivo thrombus development.

Intermetallic Pd3 X (X= Ti and Zr) nanocrystals for electro-oxidation of alcohols and formic acid in alkaline and acidic media.

Two highly active and stable Pd-based intermetallic nanocrystals with early d-metals Pd3Ti and Pd3Zr have been developed. The nanocrystals are synthesized by co-reduction of the respective salts of Pd and Ti/Zr. Hard X-ray photoemission Spectroscopy (HAXPES) analysis of the nanocrystals indicates that the electronic properties of Pd are modified significantly, as evident from the lowering of the d-band center of Pd. The intermetallic nanocrystals dispersed in Vulcan carbon, Pd3Ti/C and Pd3Zr/C, exhibit improved electrocatalytic activity towards methanol and ethanol oxidation in an alkaline medium (0.5 M KOH), compared to those of commercially available catalysts such as Pd/C, Pt/C, and Pt3Sn/C. In addition, Pd3Ti/C and Pd3Zr/C show significantly higher activity towards the oxidation of formic acid in an acidic medium (0.5 M H2SO4), compared to those of Pd/C and Pt/C. The modification of the d-band center of Pd as a result of the alloying of Pd with the early d-metals Ti and Zr may be responsible for the enhanced catalytic activity.

Synthesis and Characterization of Biobased Polyesters Containing Anthraquinones Derived from Gallic Acid.

To study the effects of the main and side chains on the physical properties of polyesters containing anthraquinone substituents, two types of 1,5-dihydroxy-2,3,6,7-tetraalkoxyanthraquinones (DHTAAQs) were prepared from gallic acid, a major component of hydrolyzable tannins, and polymerized with five dicarboxylic dichlorides by interfacial polymerization. The solubility of the fabricated polyesters was strongly affected by the alkoxy side chains of the DHTAAQ units. Conversely, their thermal decomposition behavior depended on the structure of the dicarboxylate units. The thermal properties of the anthraquinone-based polyesters were influenced by both the dicarboxylate units and alkoxy groups, and their glass transition temperature could be controlled over a wide range (81-308 °C). To design DHTAAQ-based polyesters with adequate solubility and high heat resistance, it is preferable that first suitable alkoxy groups are selected to provide the necessary solubility, and then appropriate aromatic dicarboxylate units are chosen to obtain the required thermal properties.

Altered activation of integrin ɑIIbß3 on platelets irradiated with ultraviolet C from pathogen-reducing xenon flash.

Irradiation of platelets with filtered xenon (fXe) flash for pathogen inactivation increases PAC-1 binding, but does not cause discernible aggregation. We aimed to determine whether PAC-1-positive platelets irradiated with fXe flash can bind to fibrinogen. Apheresis-collected platelets (Aph-PLTs) were irradiated with fXe flash (fXe-PLTs). Activation of integrin αIIbß3 was determined by the binding of PAC-1, fibrinogen Alexa Fluor 488-conjugate (fibrinogen-AF488), and anti-fibrinogen antibody (clone 9F9) using flow cytometry under resting or ADP-stimulated conditions. PAC-1 binding to fXe-PLTs increased in an fXe flash dose-dependent manner. The fraction of PAC-1 binding to fXe-PLTs suspended in either phosphate-buffered saline (PBS) or plasma was larger than that to Aph-PLTs in a resting state. However, no difference of fibrinogen-AF488 binding between fXe-PLTs and Aph-PLTs in PBS was observed under either resting or ADP-stimulated conditions. The binding of anti-fibrinogen to fXe-PLTs in plasma was marginally increased compared with Aph-PLTs, but the magnitude of the positive fraction was significantly smaller than that of PAC-1. Pathogen-inactivating fXe irradiation per se did not induce fibrinogen binding to platelets, while PAC-1 binding was increased in a resting state. On the other hand, the fraction of fibrinogen binding was equivalent to that of PAC-1 under ADP-stimulated conditions.

Restored response to ADP downstream of purinergic P2Y12 receptor in apheresis platelets after pathogen-reducing xenon flash treatment.

BACKGROUND: Our previous study revealed that pathogen-reducing filtered xenon flash-treated platelets (fXe-PLTs) showed sustained aggregation in response to adenosine diphosphate (ADP), but apheresis-collected PLTs (Aph-PLTs) showed reversible aggregation. STUDY DESIGN AND METHODS: Aph-PLTs, fXe-PLTs, and freshly prepared PLTs (PRP-PLTs) from whole blood were used to investigate the following responses to ADP: concentration response and effects of ADP receptor antagonists on aggregation, the cytosolic calcium (Ca2+ ) flux downstream of P2Y1 receptor signaling, and phosphorylation of vasodilator-stimulated phosphoprotein (VASP) and signaling intermediate protein Akt downstream of the P2Y12 receptor. RESULTS: The aggregation of Aph-PLTs by ADP (10 µM) changed from reversible to sustained in an fXe flash dose-dependent manner. The concentration-response curve of Aph-PLTs showed a fivefold higher 50% effective concentration compared with PRP-PLTs, and fXe treatment decreased it to threefold. While the basal Ca2+ level was higher both in Aph- and fXe-PLTs than in PRP-PLTs, the increase of cytosolic Ca2+ by ADP remained unchanged in Aph- and PRP-PLTs, but was slightly reduced in fXe-PLTs. Although the forskolin-induced VASP phosphorylation was significantly reduced in Aph-PLTs, and partially restored by the fXe treatment, ADP stimulation attenuated this phosphorylation to an equivalent extent among the three PLT types. The ADP-stimulated time-dependent Akt phosphorylation was weak in Aph-PLTs, whereas fXe-PLTs and PRP-PLTs showed a marked increase. CONCLUSION: These results indicate that the reversible aggregation of Aph-PLTs is the consequence of insufficient Akt phosphorylation. The fXe treatment restores the increase of phosphorylated Akt, resulting in the sustained aggregation of fXe-PLTs similar to those of PRP-PLTs.

Pulsed xenon flash treatment inactivates bacteria in apheresis platelet concentrates while preserving in vitro quality and functionality.

BACKGROUND: Pulsed xenon (Xe) flash without any photoreactive compounds has been shown to inactivate a type of bacteria spiked into platelet (PLT) suspension in plasma, but enhanced the PLT storage lesion (PSL). Predicting reduction of PSL with increasing bactericidal ability, pulsed Xe flash was filtered through a band-stop filter, which excluded ultraviolet (UV)A, UVB, and visible light. STUDY DESIGN AND METHODS: Apheresis PLT concentrates (PCs) inoculated with bacteria were irradiated with filtered Xe flash (fXe treatment). For in vitro functional quality assessment, PLT aggregation and thrombin generation together with other assays that monitor the PSL were investigated. RESULTS: Staphylococcus aureus and Streptococcus dysgalactiae could be inactivated without regrowth during 6 days of storage. PC variables, such as PLT count, concentrations of soluble CD40 ligand, and ratio of aggregated PLTs, were not significantly different between fXe-treated and untreated PCs after 6 days of storage, while PAC-1 binding increased in the fXe-treated PLTs. Responsiveness of fXe-treated PLTs to ADP was maintained over a 6-day storage period as shown by the up regulation of P-selectin expression and induction of both integrin αIIbß3 conformational change and PLT aggregation. The fXe-treated PLTs showed a sustained aggregation curve in response to ADP, whereas untreated PLTs transiently aggregated and then subsequently dissociated. Thrombin-generating kinetics of fXe-treated PLTs via PLT membrane surface were equivalent to those of untreated PLTs. CONCLUSIONS: The fXe treatment inactivated bacteria in apheresis PCs in plasma without additional chemical compounds. The fXe-treated PCs retained acceptable in vitro properties of PC quality and PLT functionality.

Reduction of bacteria and human immunodeficiency virus Type 1 infectivity of platelet suspension in plasma using xenon flash-pulse light in a bench-scale trial.

BACKGROUND: Current pathogen reduction systems for platelet concentrates (PCs) require addition of chemical compounds and/or reduction of plasma content in PCs. We have investigated a new method using xenon (Xe) flash-pulse light without additional compounds or plasma replacement. STUDY DESIGN AND METHODS: An aliquot of apheresis platelets (PLTs) in plasma inoculated with bacteria or human immunodeficiency virus Type 1 (HIV-1) was irradiated with Xe flash-pulse light (Xe flash phototreatment). Bacterial growth was monitored up to 6 days of storage, whereas HIV-1 infectivity was assayed just after treatment. Pairs of Xe flash-phototreated and untreated PCs were examined for PLT lesion during the storage period. RESULTS: Under the current conditions, a low titer (1.8 colony-forming units [CFUs]/mL) of Staphylococcus aureus did not proliferate during the 6-day storage period, but grew in some cases at high-titer (24.0 CFUs/mL) inoculation. HIV-1 infectivity was reduced by 1.8 log. PLT recovery of the treated PCs was lower than untreated ones. An increase of mean PLT volume and glucose consumption, together with a decrease of hypotonic shock response and pH, were enhanced by the treatment. CD62P- and PAC-1-positive PLTs increased after the treatment, indicating the induction of PLT activation. Among biologic response modifiers, soluble CD40 ligand was significantly increased in the treated PCs on Day 6. CONCLUSIONS: Xe flash phototreatment could prevent bacterial proliferation and reduce HIV-1 infectivity in 100% plasma PCs without any additional compounds, but enhanced PLT storage lesions. Further improvement is required to increase the potency of pathogen inactivation with reducing PLT damage.

CO tolerance of Pt/FeOx catalyst in both thermal catalytic H2 oxidation and electrochemical CO oxidation: the effect of Pt deficit electron state.

CO poisoning of Pt catalysts is one of the major challenges to the commercialization of proton exchange membrane fuel cells. One promising solution is to develop CO-tolerant Pt-based catalysts. A facilely synthesized Pt/FeOx catalyst exhibited outstanding CO tolerance in the oxidation of H2 and electrochemical CO stripping. Light-off temperature of H2O formation over Pt/FeOx was achieved even below 30 °C in the presence of 3000 ppm CO at a space velocity of 18 000 mL g-1cat h-1. For the electrochemical oxidation of CO, the onset and peak potentials decreased by 0.17 V and 0.10 V, respectively, in comparison with those of commercial Pt/C. More importantly, by a combination of hard X-ray photoemission spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies it was found that the decreased electron density of Pt in Pt/FeOx enhanced the mobility of adsorbed CO, suppressed Pt-CO bonding and significantly increased the CO tolerance of Pt/FeOx.

Tailoring the surface-oxygen defects of a tin dioxide support towards an enhanced electrocatalytic performance of platinum nanoparticles.

Tin-dioxide nanofacets (SnO2 NFs) are crystal-engineered so that oxygen defects on the maximal {113} surface are long-range ordered to give rise to a non-occupied defect band (DB) in the bandgap. SnO2 NFs-supported platinum-nanoparticles exhibit an enhanced ethanol-electrooxidation activity due to the promoted charge-transport via the DB at the metal-semiconductor interface.

Nucleus Ruber of Actinopterygians.

Nucleus ruber is known as an important supraspinal center that controls forelimb movements in tetrapods, and the rubral homologue may serve similar functions in fishes (motor control of pectoral fin). However, two apparently different structures have been identified as 'nucleus ruber' in actinopterygians. One is nucleus ruber of Goldstein (1905) (NRg), and the other nucleus ruber of Nieuwenhuys and Pouwels (1983) (NRnp). It remains unclear whether one of these nuclei (or perhaps both) is homologous to tetrapod nucleus ruber. To resolve this issue from a phylogenetic point of view, we have investigated the distribution of tegmental neurons retrogradely labeled from the spinal cord in eight actinopterygian species. We also investigated the presence/absence of the two nuclei with Nissl- or Bodian-stained brain section series of an additional 28 actinopterygian species by comparing the morphological features of candidate rubral neurons with those of neurons revealed by the tracer studies. Based on these analyses, the NRg was identified in all actinopterygians investigated in the present study, while the NRnp appears to be absent in basal actinopterygians. The phylogenetic distribution pattern indicates that the NRg is the more likely homologue of nucleus ruber, and the NRnp may be a derived nucleus that emerged during the course of actinopterygian evolution.

Enantioselective Total Synthesis of the Proposed Structure of Furan-Containing Polyketide.

Enantioselective total synthesis of the proposed structure of furan-containing polyketide was accomplished. The key features include a chemo- and enantioselective epoxidation of 1,4-cyclohexadiene by Shi asymmetric epoxidation, a regioselective epoxide ring opening, chemo- and diastereoselective dihydroxylation of the conjugated dienone derivative, and vinylation of the lactone accompanied by formation of the furan ring.

The Total Synthesis of (±)-Naupliolide: A Tetracyclic Sesquiterpene Lactone.

The first total synthesis of (±)-naupliolide has been achieved. The synthetic method includes a Simmons-Smith cyclopropanation of an allyl alcohol, diastereoselective cleavage of a benzylidene acetal group, radical cyclization of an aldehyde with a cyclopropane ring, and construction of an eight-membered ring by ring-closing metathesis.