Daphmanidins C and D, novel pentacyclic alkaloids from Daphniphyllum teijsmanii

[structure: see text] Two novel alkaloids with an unprecedented fused-pentacyclic skeleton, daphmanidins C (1) and D (2), have been isolated from the leaves of Daphniphyllum teijsmanii, and the structures were elucidated on the basis of spectroscopic data. The relative stereochemistry of 1 and 2 was assigned by combination of NOESY correlations and a simulation analysis. Daphmanidin C (1) elevated activity of NGF biosynthesis.     

Mechanism of deflagration-to-detonation transitions above repeated obstacles

Experiments are carried out to investigate the mechanism of the deflagration-to-detonation transition (DDT). Because, this mechanism has relevance to safety issues in industries, where combustible premixed gases are in general use. A stoichiometric gas of oxygen and hydrogen (oxy-hydrogen) is ignited in a tube, repeated obstacles are installed, and the DDT behaviours are visualized using a high-speed video camera. The pitch and height of the repeated obstacles and the initial pressure of the oxy-hydrogen premixed gas are varied in an attempt to obtain the optimum conditions that cause DDT a short distance from the ignition source. The experiments identified DDT as being essentially caused by one of the following mechanisms: (1) A deflagration wave is accelerated in terms of a vortex, which is generated behind the obstacle, and the flame acceleration induces a secondary shock wave. Eventually, the shock–flame interaction ahead of the obstacle causes DDT via a very strong local explosion. (2) Each shock wave generated by relatively weak local explosions between the obstacles is not sufficient to cause DDT directly, but DDT results from an accumulation of shock waves. The detonation induction distance is also examined, taking into account the physical and chemical parameters of the obstacles and the oxy-hydrogen premixed gas.     

Cavitation phenomena in extracorporeal microexplosion lithotripsy

An experimental investigation was made of cavitation phenomena induced by underwater shock wave focusing applied to the extracorporeal microexplosion lithotripsy (microexplosion ESWL). Firstly an underwater microexplosion generated by detonation of a 10 mg silver azide pellet was studied and secondly underwater shock focusing and its induced cavitation phenomena were investgated. Underwater shock wave was focused by using a semi-ellipsoidal reflector in which a shock wave generated at the first focal point of the reflector was reflected and focused at the second focal point. It is found that an explosion product gas bubble did not produce any distinct rebound shocks. Meantime cavitation appeared after shock focusing at the second focal point where expansion waves originated at the exit of the reflector were simultaneously collected. A shock/bubble interaction is found to contribute not only to urinary tract stone disintegration but also tissue damage. The cavitation effect associated with the microexplosion ESWL was weaker in comparison with a spark discharge ESWL. The microexplosion ESWL is an effective method which can minimize the number of shock exposures hence decreasing tissue damage by conducting precise positioning of urinary tract stones.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

In Vivo Photoacoustic Monitoring of Photosensitizer Distribution in Burned Skin for Antibacterial Photodynamic Therapy

For efficient antibacterial photodynamic therapy for wounds, information on the distribution of a photosensitizer in tissue is important, but conventional fluorescence measurement does not provide depth-resolved information. We previously proposed in vivo photoacoustic (PA) depth profiling of a photosensitizer, but the contrast of PA signals was not sufficiently high, mainly due to light absorption by blood in tissue. In this study, we performed dual-wavelength PA measurement; green light and red light were used to excite blood and photosensitzer, respectively, and the former signal was subtracted from the latter signal to compensate a blood-associated component. Methylene blue or porfimer sodium solution was injected into subcutaneous tissue in rats with deep dermal burn and two-dimensional PA measurement was performed. The signal subtraction diminished not only the signal originating from blood but also the signal originating from the stratum corneum and acoustic reflection noise, creating a high-contrast PA image. The distribution of PA signals was confirmed to coincide well with the distribution of photosensitizer-originating fluorescence measured for tissue biopsied after the PA measurement, demonstrating the validity of this method for in vivo photosensitizer dosimetry. On the basis of this method, temporal behaviors of two photosensitizers were compared.     

Dissipative and Autonomous Square‐Wave Self‐Oscillation of a Macroscopic Hybrid Self‐Assembly under Continuous Light Irradiation

Building a bottom‐up supramolecular system to perform continuously autonomous motions will pave the way for the next generation of biomimetic mechanical systems. In biological systems, hierarchical molecular synchronization underlies the generation of spatio‐temporal patterns with dissipative structures. However, it remains difficult to build such self‐organized working objects via artificial techniques. Herein, we show the first example of a square‐wave limit‐cycle self‐oscillatory motion of a noncovalent assembly of oleic acid and an azobenzene derivative. The assembly steadily flips under continuous blue‐light irradiation. Mechanical self‐oscillation is established by successively alternating photoisomerization processes and multi‐stable phase transitions. These results offer a fundamental strategy for creating a supramolecular motor that works progressively under the operation of molecule‐based machines.     

Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe(2+) and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths-661 (Cy5) or 568 (Cy3)nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.     

Dihydrobenzofurans as cannabinoid receptor ligands from Cordyceps annullata,an entomopathogenic fungus cultivated in the presence of an HDAC inhibitor

The secondary metabolite production of Cordyceps annullata, an entomopathogenic fungus, was clearly enhanced by the addition of suberoyl bis-hydroxamic acid (SBHA), a histone deacetylase (HDAC) inhibitor, to the culture medium. Four new 2,3-dihydrobenzofurans, annullatins A–D (1–4), and a new aromatic polyketide, annullatin E (5) were isolated from the culture medium, and the structures, including the absolute stereochemistries, were determined by spectroscopic analysis, vibrational circular dichroism (VCD), and chemical transformations. Annullatin A (1) exhibited potent agonistic activity toward the cannabinoid receptors CB1 and CB2. Annullatin B (2) and D (4) displayed CB1 agonistic activity and CB2 inverse agonistic activity.     

Nuclear magnetism of sub-monolayer solid He on graphite

Nuclear magnetization has been measured with NMR down to temperatures around 0.1 mK for sub-monolayer solid ³He formed on graphite preplated with two layers of HD. The data for the commensurate phase show no evidence of a magnetic transition and a rather slow increase of the magnetization even at ultra-low temperature (0.15 mK), much lower than the antiferromagnetic exchange interaction of −6.3 mK.     

Low-temperature magnetization of submonolayer 3He adsorbed on HD preplated graphite

NMR studies of submonolayer 3He adsorbed on a bilayer of HD preplated graphite have been made down to 100 &mgr;K, which is more than 1 order of magnitude smaller than the exchange energy ( J). In the highly frustrated antiferromagnetic solid region, the magnetization obeys a Curie-Weiss law even at temperatures around J and then increases gradually down to 100 &mgr;K. Nevertheless, it does not show any anomalous behavior corresponding to a spin gap. The normalized magnetization versus the reduced temperature ( T/J) is independent of the density just after solidification. This is consistent with the result in the high-temperature region, that the main multiple-spin exchanges have a similar density dependence.     

Observation of rotational population transfer effect for an HF chemical laser

When a CO₂ gas absorption cell was placed within the optical cavity of a low pressure pulsed HF laser, the specific vibration- rotation line of the HF laser disappeared, which influenced both the intensity and pulse duration of the neighbouring lines. This behavior strongly depends upon the rotational population transfer in HF. By measuring the time response of this behavior, it was found that the rate constant for the rotational population transfer was in the range of 10⁷ s^-1 torr^-1 for the SF₆/H₂ lasing mixture.