Study of hydantoin. III . Mass spectrometric behaviour in the electron impact of 2-imino-4-thiazolidinone derivatives

The mass spectral decomposition modes of a series of 2-imino-4-thiazolidinone derivatives are reported and discussed. The fragmentation patterns and mechanisms postulated have been confirmed by the analysis of the MIKE spectra and using DADI technique and the effects of heteroatoms and substituents on the MIKE spectrum of these compounds are compared with that of 3-substituted hydantoins.     

Magnetic nonuniformity and thermal hysteresis of magnetism in a manganite thin film

We measured the chemical and magnetic depth profiles of a single crystalline (La(1-x)Pr(x))(1-y)Ca(y)MnO(3-δ) (x=0.52±0.05, y=0.23±0.04, δ=0.14±0.10) film grown on a NdGaO(3) substrate using x-ray reflectometry, electron microscopy, electron energy-loss spectroscopy, and polarized neutron reflectometry. Our data indicate that the film exhibits coexistence of different magnetic phases as a function of depth. The magnetic depth profile is correlated with a variation of chemical composition with depth. The thermal hysteresis of ferromagnetic order in the film suggests a first-order ferromagnetic transition at low temperatures.     

Mathematical modelling of the catalyst layer of a polymer electrolyte fuel cell

In this paper, we derive a mathematical model for the cathodecatalyst layer of a polymer electrolyte fuel cell. The modelexplicitly incorporates the restriction placed on oxygen inreaching the reaction sites, capturing the experimentally observedfall in the current density to a limiting value at low cellvoltages. Temperature variations and interfacial transfer ofO₂ between the dissolved and gas phases are also included. Boundson the solutions are derived from which we provide a rigourousproof that the model admits a solution. Of particular interestare the maximum and minimum attainable values. We perform anasymptotic analysis in several limits inherent in the problemby identifying important groupings of parameters. This analysisreveals a number of key relationships between the solutions,including the current density, and the composition of the layer.A comparison of numerically computed solutions and asymptoticsolutions shows very good agreement. Implications of the resultsare discussed and future work is outlined.     

Active control of supersonic impingement tones using steady and pulsed microjets

In recent years, it has been demonstrated that direct microjet injection into the shear layer of the main jet disrupts the feedback loop inherent in high speed impinging jet flows, thereby significantly reducing the adverse effects. The amount of noise reduced by microjet actuation is known to be dependent on nozzle operating conditions. In this paper, two active control strategies using microjets are suggested to maintain a uniform, reliable, and optimal reduction of these tones over the entire range of operating conditions. In the first method, a quasi-closed loop control strategy is proposed using steady microjet injection and the proper orthogonal decomposition (POD) algorithm. The most energetic spatial mode of the unsteady pressure along the nozzle diameter is captured using the POD, which in turn is used to determine the distribution of microjet intensity along the nozzle exit. Preliminary experimental results from a STOVL supersonic jet facility at Mach 1.5 show that the quasi-closed loop control strategy, in some cases, provides an additional 8–10 dB reduction compared to axisymmetric injection at the desired operating conditions. The second method consists of a pulsed microjet injection, motivated by the need to further improve the noise suppression. It was observed that the pulsed microjet was able to bring about the same noise reduction as steady injection using approximately 40% of the corresponding mass flow rate of the steady microjet case. Moreover, as the duty cycle increased, the performance of pulsed injection was further enhanced and was observed to completely eliminate the impinging tones at all operating conditions.     

Low energy proton beam induces tumor cell apoptosis through reactive oxygen species and activation of caspases

Proton beam is useful to target tumor tissue sparing normal cells by allowing precise dose only into tumor cells. However, the cellular and molecular mechanisms by which proton beam induces tumor cell death are still undefined. We irradiated three different tumor cells (LLC, HepG2, and Molt-4) with low energy proton beam (35 MeV) with spread out Bragg peak (SOBP) in vitro, and investigated cell death by MTT or CCK-8 assay at 24 h after irradiation. LLC and HepG2 cells were sensitive to proton beam at over 10 Gy to induce apoptosis whereas Molt-4 showed rather low sensitivity. Relative biological effectiveness (RBE) values for the death rate relative to gamma-ray were ranged from 1.1 to 2.3 in LLC and HepG2 but from 0.3 to 0.7 in Molt-4 at 11 d after irradiation by colony formation assay. The typical apoptotic nuclear DNA morphological pattern was observed by staining with 4'-6-diamidino-2-phenylindole (DAPI). Tiny fragmented DNA was observed in HepG2 but not in Molt-4 by the treatment of proton in apoptotic DNA fragment assay. By FACS analysis after stained with FITC-Annexin-V, early as well as median apoptotic fractions were clearly increased by proton treatment. Proton beam-irradiated tumor cells induced a cleavage of poly (ADP-ribose) polymerase-1 (PARP-1) and procaspases-3 and -9. Activity of caspases was highly enhanced after proton beam irradiation. Reactive oxygen species (ROS) were significantly increased and N-acetyl cysteine pretreatment restored the apoptotic cell death induced by proton beam. Furthermore, p38 and JNK but not ERK were activated by proton and dominant negative mutants of p38 and JNK revived proton-induced apoptosis, suggesting that p38 and JNK pathway may be activated through ROS to activate apoptosis. In conclusion, our data clearly showed that single treatment of low energy proton beam with SOBP increased ROS and induced cell death of solid tumor cells (LLC and HepG2) in an apoptotic cell death program by the induction of caspases activities.     

THE EFFECT OF DEUTERIUM OXIDE ON THE FLUORESCENCE AND PHOTOTRANSFORMATION OF 124 kDALTON PHYTOCHROME*

Abstract— To probe the nature of primary photoprocess and the mechanism of the phototransformation of undegraded 124 kDa oat phytochrome, solvent deuterium isotope effects on the fluorescence and phototransformation of phytochrome have been investigated. The fluorescence intensity and lifetime of phytochrome (P_r form) are greater in D₂0-buffer than in H₂O-buffer, suggesting a possible involvement of proton transfer in the primary photoprocess of phytochrome. Although the photostationary equilibrium (P_r to P_fr ratio) was not altered by deuterium oxide, in contrast to degraded phytochrome, the rate constants of both transformations, P_r→ P_fr and P_fr→ P_r were enhanced by up to 24%. The P_r to P_fr phototransformation of degraded phytochrome, however, was retarded by about the same percentage in D₂O. These opposite effects of D₂O with degraded and undegraded phytochromes underscore the fact that the P_r form from the former reverts to the P_r form in the dark, apparently catalyzed by deuterated general and/or conjugate acidic group(s). With the degraded phytochrome the deuterium oxide enhancement of the rate of dark reversion was approximately 2-fold (Sarkar and Song, 1981). Both the fluorescence intensity and the rates of phototransformation of phytochrome were enhanced in D₂O with successive photocyclings (P_r→ P_fr→ P_r→ P_fr→ P_r etc.) with alternating red and far-red irradiation. It has been proposed that successive photocycling of phytochrome in D₂O results in proton-deuteron exchange in the partially exposed P_tr chromophore and/or its surrounding amino acid residues.