Collisional quenching of metastable states of antiprotonic helium by hydrogen and deuterium molecules

The quenching of metastable states of antiprotonic helium by collisions with hydrogen and deuterium molecules was studied. A systematic investigation of the delayed annihilation time spectra at various H₂ and D₂ admixture ratios at the ppm level revealed characteristic changes of their shape, which indicated a strong principal and orbital quantum number dependent quenching of levels in both cases. Applying a laser spectroscopy technique to measure the lifetimes of individual states and cascades we deduced H₂ and D₂ quenching cross-sections for the states (n, l )= (39, 35) and (37, 34). These cross-sections establish for D₂ molecules the strong increase of the quenching efficiency with increasing principal quantum number n of the state under investigation previously reported for the case of H₂ admixtures. Our experiments indicate that the low-n state (37, 34) is somewhat less affected by D₂ than by H₂, while the high-n state (39, 35) is equally quenched by both isotopes. Received 2 October 2000     

Research on the pig liver esterase (PLE)-catalyzed kinetic resolution of half-esters derived from prochiral diesters

The pig liver esterase (PLE)-catalyzed kinetic resolution of half-esters derived from prochiral diesters is described. Generally, the PLE-catalyzed enantioselective hydrolysis of prochiral diesters affords the corresponding half-esters in high yield, because further hydrolysis of the half-esters does not typically occur. However, we found that some half-esters undergo PLE-catalyzed hydrolysis when they are gradually added to a PLE suspension in a potassium phosphate buffer at pH 8.0 via a syringe pump, leading to the kinetic resolution of the half-esters.     

Enantioselective Total Synthesis of (+)‐Ophiobolin A

The enantioselective total synthesis of (+)‐ophiobolin A is described. This total synthesis features the construction of the spiro CD ring of (+)‐ophiobolin A through a stereoselective intramolecular Hosomi–Sakurai cyclization reaction, the joining of the A ring to the CD ring by using a reaction reported by Utimoto, and the construction of the ophiobolin eight‐membered carbocyclic ring through ring‐closing metathesis (RCM), which was performed for the first time in this study. This successful RCM reaction required the use of a substrate that contained either a benzyloxy or a methoxymethoxy group at the C5 position and either an isopropenyl group or its hydroxylated form at the C6 position.     

Evaluation of new pasty-type implantable devices consisting of poly(epsilon-caprolactone/delta-valerolactone) and Estracyt or estramustine.

Biodegradable pasty-type copolyesters with a relatively low molecular weight of 4500 were synthesized by direct copolycondensation of epsilon-caprolactone (CL) and delta-valerolactone (VL) in the absence of catalysts to evaluate in vivo capabilities of the polymer for implantable controlled release devices in drug delivery systems. The devices in cylindrical shape were prepared by the melt-pressing technique using pasty-type copoly(CL/VL) with 53 mol% CL unit, in which Estracyt and estramustine were used as a water soluble and insoluble drug, respectively. The degradation and drug release in vivo of the devices were examined by subcutaneous implantation in the backs of male rats. The degradation of the device was remarkably accelerated by the presence of hydrophilic Estracyt, and was slightly suppressed by hydrohobic estramustine. The estramustine release profile roughly corresponded to the polymer degradation one. It was found that the degradation of the polymer in the device was affected by hydrophilicity of the drug. A reasonable release of estramustine from the device was kept for a period of more than 20 weeks. Furthermore, the release of the drugs in vivo was able to lead to an atrophy of accessory sex organs such as ventral prostates (VP) and right-side seminal vesicle (SV), resulting in pharmacological influence.     

Elimination of ingredients effect to improve the detection of anti HIV-1 p24 antibody in human serum using SPR apparatus.

Highly sensitive detection of proteins in serum becomes difficult in some cases during surface plasmon resonance (SPR) measurements, because some ingredients in the serum hugely enhance non-specific reactions on the sensing chip of SPR. It is well recognized that the antibody against core protein p24 of HIV in serum is one of the most important proteins in the accurate diagnosis of infection with HIV. In this study, we could attain the accurate detection of anti p24 antibody in human serum by eliminating the serious effects of the ingredients in serum on the measurement of SPR by employing these procedures: 1) blocking the gold surface of the sensing chip with human serum and 2) heating the serum sample at 56 degrees C for 30 min. Without these treatments, the signal of SPR was considerably suppressed on the measurements of the anti p24 antibody which contained human serum, making the accurate detection difficult. However, with introducing the above two treatments, the sensing of anti p24 antibody in human serum was improved, while a small non-specific reaction was still observed. By removing the non-specific reaction caused by the ingredients in the serum, we could accurately measure the antibody for p24 in human serum sample over the range from 1 to 20 micrograms/ml.     

Spontaneous splitting of a quadruply charged vortex

We studied the splitting instability of a quadruply charged vortex both experimentally and theoretically. The density defect, which is a signature of the vortex core, is experimentally observed to deform into a linear shape. The deformed defect is theoretically confirmed to be an array of four linearly aligned singly charged vortices. The array of vortices rotates and precesses simultaneously with different angular velocities. The initial state of the system is not rotationally symmetric, which enables spontaneous splitting without external perturbations.     

Concise and stereoselective synthesis of 2,5- and 2,4-disubstituted thiazole amino acid subunits for synthesizing thiazole-containing peptides

A concise, highly stereoselective synthesis of 2,4- and 2,5-disubstituted thiazole amino acids was developed. These are important building blocks for various biologically active thiazole-containing natural peptides and their regioisomeric analogues. The fundamental reactions are diastereoselective addition of (4- or 5-bromothiazol-2-yl)lithium to N-tert-butanesulfinyl imine with subsequent Pd-catalyzed phenoxycarbonylation.     

Effects of 230 MeV Au irradiation on Bi2Sr2CaCu2Ox

Bi₂Sr₂CaCu₂O_x tapes were irradiated using 230 MeV Au¹⁴⁺ ions. Columnar defects were presumably produced due to irradiation. Zero-field-cooling (ZFC) magnetization increased up to a fluence of 1.6 × 10¹¹ Au⁺/cm², but field-cooling (FC) magnetization decreased, indicating the strong pinning effects resulting from the columnar defects. The critical current density as well as the irreversibility field, obtained from the hysteresis loops, were enhanced. Irreversibility fields are fitted by H_irr = A exp(−T/T_A). An effective activation energy for flux motion was obtained from the measurements of magnetization relaxation. The features of flux pinning as a result of the columnar defects were compared with those of point defects brought about by 120 MeV O⁷⁺ irradiation.     

Evaluation of Furan Photooxygenation as a Device for Construction of the Zaragozic Acid (Squalestatin) Core

A practical application of the photooxygenation chemistry of 3-substituted furans to construction of the zaragozic acid/squalestatin backbone is described. Although addition of 3-lithiofuran to the tartrate-derived aldehyde 7 proceeds without chelation control to give a 1:1 mixture of diastereomeric alcohols 8, it is demonstrated initially that ready conversion to the polyfunctional intermediate 10 is possible by sequential treatment of 9 with singlet oxygen, sodium borohydride, and triisopropylsilyl triflate. The actual enantiocontrolled route consisted of oxidation of 8 to the ketone and Wittig olefination of the latter in advance of asymmetric dihydroxylation with AD-mix-beta. Once this series of transformations had been accomplished, formation of the target product 30 was realized by an entirely comparable photooxygenation.