Synthesis of 1-beta-O-acyl glucuronides of diclofenac, mefenamic acid and (S)-naproxen by the chemo-selective enzymatic removal of protecting groups from the corresponding methyl acetyl derivatives

Using a straightforward chemo-enzymatic procedure, 1-beta-O-acyl glucuronides of three non-steroidal anti-inflammatory drugs, diclofenac (DF) 5, mefenamic acid (MF) 6 and (S)-naproxen (NP) 7, were prepared. Caesium salts of these carboxylic acid drugs reacted with commercially available methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-alpha-D-glucopyranuronate 4 to give exclusively the corresponding 1-beta-O-acyl glucuronides 8-10 in moderate yields. The protecting acetyl (for -OH group) and methyl ester (for -CO2H group) groups of each sugar moiety were easily removed to provide the corresponding free 1-beta-O-acyl glucuronides 1-3 in high yields. Deprotection was achieved through effective enzyme-catalysed chemo-selective hydrolyses of the acetyl groups using lipase AS Amano (LAS), and of the methyl ester group using esterase from porcine liver (PLE).     

Determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell

A method is described for determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell (ID–ICP–ORCMS). Sediment samples were digested with HNO₃, HClO₄, and HF, and the digestion included an elaborate evaporation process to remove bromine from the digested solution. Simple strong cation-exchange disk filtration was used to remove rare earth elements (REE) from the digested solution, because REE²⁺ seriously interfere with Se isotopes (i.e. ¹⁵⁶Gd²⁺ with ⁷⁸Se⁺, ¹⁶⁰Gd²⁺ with ⁸⁰Se⁺). Addition of acetic acid to the filtrate was examined to improve the sensitivity of ICP–ORCMS measurement of Se⁺ by means of a carbon-enhancement effect. The interfering for selenium isotopes were almost eliminated by use of H₂ as reaction gas. Interference from BrH⁺ formed in the reaction cell was negligible because the Br was removed in the evaporation process. Approximately 99.5% of REE were removed by cation-exchange disk filtration yet more than 99% of Se remained in the filtrate solution. The intensity for Se⁺ was enhanced approximately fourfold by addition of 5% (v/v) of acetic acid whereas that for was barely enhanced. Measured ⁸⁰Se/⁷⁸Se ratios in unspiked digested solutions of the sample were in good agreement with that for an Se standard solution. The analytical results for Se in the certified reference materials MESS-3 and PACS-1 were in good agreement with their certified values, with small uncertainties.      

Photo-control of kinesin-microtubule motility using caged peptides derived from the kinesin C-terminus domain

To design a nanoscale biodevice that can be controlled by an external stimulus, we have introduced photochemical switching peptides derived from the kinesin C-terminus domain into the kinesin-microtubule in vitro motility system.     

Coevolutionary,coexisting learning and teaching agents model for prisoner’s dilemma games enhancing cooperation with assortative heterogeneous networks

Unlike other natural network systems, assortativity can be observed in most human social networks, although it has been reported that a social dilemma situation represented by the prisoner’s dilemma favors dissortativity to enhance cooperation. We established a new coevolutionary model for both agents’ strategy and network topology, where teaching and learning agents coexist. Remarkably, this model enables agents’ enhancing cooperation more than a learners-only model on a time-frozen scale-free network and produces an underlying assortative network with a fair degree of power-law distribution. The model may imply how and why assortative networks are adaptive in human society.     

Tissue gadolinium deposition in renally impaired rats exposed to different gadolinium-based MRI contrast agents: Evaluation with inductively coupled plasma mass spectrometry (ICP-MS)

ObjectivesTo quantify tissue gadolinium (Gd) deposition in renally impaired rats exposed to Gd-EOB-DTPA and other Gd-based MRI contrast agents by means of inductively coupled plasma mass spectrometry (ICP-MS), and to compare the differences in distribution among major organs as possible triggers for nephrogenic systemic fibrosis (NSF).MethodsA total of 15 renally impaired rats were injected with Gd-EOB-DTPA, Gd-DTPA-BMA and Gd-HP-DO3A. Gd contents of skin, liver, kidney, lung, heart, spleen, diaphragm and femoral muscle were measured by inductively coupled plasma mass spectrometry (ICP-MS). Histological assessment was also conducted.ResultsTissue Gd deposition in all organs was significantly higher (P = 0.005 ~ 0.009) in the Gd-DTPA-BMA group than in the Gd-HP-DO3A and Gd-EOB-DTPA groups. In the Gd-DTPA-BMA group, Gd was predominantly deposited in kidney (1306 ± 605.7 μg/g), followed by skin, liver, lung, spleen, femoral muscle, diaphragm and heart. Comparing Gd-HP-DO3A and Gd-EOB-DTPA groups, Gd depositions in the kidney, liver and lung were significantly lower (P = 0.009 ~ 0.011) in the Gd-EOB-DTPA group than in the Gd-HP-DO3A group although no significant differences were seen for any other organs.ConclusionsGd-EOB-DTPA is a stable and safe Gd-based contrast agent (GBCA) showing lower Gd deposition in major organs in renally impaired rats, compared with other GBCAs. This fact suggests that the risk of NSF onset would be low in the use of Gd-EOB-DTPA.     

Asymptotic analysis for an extended discrete Lotka–Volterra system related to matrix eigenvalues

The integrable discrete hungry Lotka–Volterra (dhLV) system is easily transformed to the qd-type dhLV system, which resembles the recursion formula of the qd algorithm for computing matrix eigenvalues. Some of the qd-type dhLV variables play a role for assisting the time evolution of the others. This property does not appear in the original dhLV system. In this article, we first show the existence of a centre manifold for the qd-type dhLV system. With the help of the centre manifold theory, we next investigate the local convergence of the qd-type dhLV system, and then clarify the monotonicity related to the qd-type dhLV variables at the final phase of the convergence.     

Front shock behavior of stable curved detonation waves in rectangular-cross-section curved channels

The propagation of curved detonation waves of gaseous explosives stabilized in rectangular-cross-section curved channels is investigated. Three types of stoichiometric test gases, C₂H₄ + 3O₂, 2H₂ + O₂, and 2C₂H₂ + 5O₂ + 7Ar, are evaluated. The ratio of the inner radius of the curved channel (r_i) to the normal detonation cell width (λ) is an important factor in stabilizing curved detonation waves. The lower boundary of stabilization is around r_i/λ = 23, regardless of the test gas. The stabilized curved detonation waves eventually attain a specific curved shape as they propagate through the curved channels. The specific curved shapes of stabilized curved detonation waves are approximately formulated, and the normal detonation velocity (D_n)?curvature (κ) relations are evaluated. The D_n nondimensionalized by the Chapman–Jouguet (CJ) detonation velocity (D_CJ) is a function of the κ nondimensionalized by λ. The D_n/D_CJ?λκ relation does not depend on the type of test gas. The propagation behavior of the stabilized curved detonation waves is controlled by the D_n/D_CJ?λκ relation. Due to this propagation characteristic, the fully-developed, stabilized curved detonation waves propagate through the curved channels while maintaining a specific curved shape with a constant angular velocity. Self-similarity is seen in the front shock shapes of the stabilized curved detonation waves with the same r_i/λ, regardless of the curved channel and test gas.     

Effect of laser intensity on fast-electron-beam divergence in solid-density plasmas

Metal foil targets were irradiated with 1 mum wavelength (lambda) laser pulses of 5 ps duration and focused intensities (I) of up to 4x10;{19} W cm;{-2}, giving values of both Ilambda;{2} and pulse duration comparable to those required for fast ignition inertial fusion. The divergence of the electrons accelerated into the target was determined from spatially resolved measurements of x-ray K_{alpha} emission and from transverse probing of the plasma formed on the back of the foils. Comparison of the divergence with other published data shows that it increases with Ilambda;{2} and is independent of pulse duration. Two-dimensional particle-in-cell simulations reproduce these results, indicating that it is a fundamental property of the laser-plasma interaction.