Determination of hyoscyamine and scopolamine in serum and urine of humans by liquid chromatography with tandem mass spectrometry

A simple method was developed for the analysis of hyoscyamine and scopolamine in human serum and urine using liquid chromatography with tandem mass spectrometry (LC/MS/MS). Hyoscyamine and scopolamine in serum and urine were cleaned up with an Oasis HLB cartridge and a PSA cartridge. The LC separation was carried out on an ODS column, using linear gradient elution with 5 mmol/L IPCC-MS3-methanol as the mobile phase. The mass spectral acquisition was done in the positive ion mode by applying selected reaction monitoring (SRM). The recoveries of hyoscyamine and scopolamine were 86.0-105% from human serum and urine fortified at 0.2 ng/mL and 10 ng/mL. The detection limits of hyoscyamine and scopolamine were 0.02 ng/mL. Four serum and three urine samples of humans poisoned by eating Datura innoxia Mill. were analyzed by this method. Hyoscyamine and scopolamine were detected at the levels of 0.45-3.5 ng/mL in all serum samples and 170-670 ng/mL in all urine samples.     

Preparations and reactions of alkyl ethers of some aldohexoses

Aldohexose, such asd-glucose,d-galactose ord-mannose, reacted with acetone to give the following O-isopropylidene derivatives: 1,2;5,6-di-O-isopropylidene-d-glucofuranose (IA), 1,2;3,4-di-O-isopropylidene-d-galactopyranose (IB) or 2,3;5,6-di-O-isopropylidene-D-mannofuranose (IC). The O-isopropylidene derivative (IA～IC) reacted with alkyl/alkenyl halogenide to yield aldohexose ether compounds containing di-O-isopropylidene group, 3-O-alkyl-1,2;5,6-di-O-isopropylidene-d-glucofuranose (II), 6-O-alkyl-1,2;3,4-di-O-isopropylidene-d-galactopyranose (III) or 1-O-alkyl-2,3;5,6-di-O-isopropylidene-d-mannofuranoside (IV), in good yields. The Williamson ether synthesis was carried out using phase-transfer catalysis (PTC). The derived aldohexose alkyl ether containing di-O-isopropylidene group was hydrolyzed to give 3-O-alkyl-1,2-O-isopropylidene-d-glucofuranose (V) as a partial hydrolysis product; the complete hydrolysis of I～IV gave, as expected, 3-O-alkyl-glucopyranose (VI), 6-O-alkyl-galactopyranose (VII) or 1-O-alkyl-mannofuranoside (VIII). Further alkylation of (V) with Mel under PTC and subsequent acid hydrolysis gave 3-O-alkyl-5,6-di-O-methyl-d-glucofuranose (X). Methanolysis of III with catalytic amounts of H₂SO₄ gave 1-O-methyl-6-O-alkyl-d-galactofuranoside (XI). The elucidation of the galactofuranoside skeleton of (XI) was determined by means of its¹³C nuclear magnetic resonance spectra. The O-alkyl aldohexoses, e.g., X and XI, were evaluated and found to be emulsifiers.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

Growth of High-Quality Pb((Zn1/3Nb2/3)0.91Ti0.09)O3 Single Crystals by Excess ZnO Addition

A high-quality single crystal of Pb((Zn_1/3Nb_2/3)_0.91Ti_0.09)O₃ (PZNT 91/9), 40 mm in diameter and 20 mm in length, was successfully grown using the solution Bridgman method with a slight excess amount of ZnO. High-quality wafers were sliced from the light-brown single crystal. No PbO inclusions or opaque areas were observed in the transparent wafers. An array probe for echocardiography was constructed with the single-crystal wafer, and its superior performance was demonstrated.     

Ether lipids based on the glyceryl ether skeleton: Present state,future potential

Lipids from natural sources consist mainly of saponifiable substances, such as glycerides, along with some unsaponifiable lipids, some of which are ether lipids. Typical ether lipids are monoalkyl ethers of glycerin, also called alkyl/alkenyl glyceryl ethers. Alkyl/alkenyl glyceryl ethers have also been reported in marine organisms and in human feces. Several chemical syntheses of such ether lipids have been reported. Typical examples are alkyl glyceryl ether formation by the addition reaction of alkyl glycidyl ether and the telomerization reaction of butadiene with glycerin and a transition metal catalyst. Characteristic chemical structures, such as terpene alkyl glyceryl ethers, archaebacterial macrocyclic ether lipids, and glyceryl ethers of condensed cyclic planar molecules, have been obtained as well. Over the past few decades, industry has shown much interest in the chemistry and application of highly branched fatty acids. For example, isostearyl glyceryl ether (GE-IS) with methyl branching in the middle chain was already known, but it is now prepared at an industrial scale by proprietary alkyl glycidyl ether methods. The characteristic behavior of GE-IS toward water, such as formation of water-in-oil emulsions containing large amounts of water and of liquid crystals, has made it applicable for use in hair and skin-care cosmetics. Based on these studies and considerations, glyceryl ether lipids, which are rarely investigated, may become one of the most important and useful lipids in the industry.     

Electron spin resonance of transparent alumina ceramics fabricated by spark plasma sintering

Transparent α‐alumina ceramics are fabricated using spark plasma sintering. Paramagnetic defects related to the optical properties of the ceramics have been investigated using electron spin resonance (ESR) analyses. An isotropic ESR signal at g = 2.003 (S = 1/2) with a linewidth of 0.5 mT is formed during sintering. The g = 2.003 signal intensity has a weak correlation with the absorbance in the visible region but does not correlate with the real in‐line transmission (RIT) at 650 nm. An ESR signal with a fine structure attributed to Fe³⁺ was detected in both the α‐Al₂O₃ starting powder and the sintered ceramic samples. The degree of c‐axis orientation of the grains has been determined using the Fe³⁺ signal intensity, which depends on the angle between the directions of the c‐axis and the applied magnetic field. The ESR analysis indicated that the c‐axis tends to be oriented in the direction of the sintering pressure. The degree of c‐axis orientation was found to correlate with the RIT in highly densified ceramics.     

Instrumentation for dual-probe scanning near-field optical microscopy

To investigate local carrier motions, we developed a dual-probe scanning near-field optical microscope (SNOM) with two fiber probes where one is for photoexcitation and the other is for light collection. This instrumentation is based on two important techniques: the design of probe structures and distance control between the sample surface and the two probes. A finite-difference time-domain method numerically analyzed and optimized the design for high efficiency photoexcitation and light collection, while a dual band modulation realized distance control. Real time detection of the oscillations of the probe tips using different frequencies independently controls the distance between the probe tip and the sample surface as well as the distance between the two probes. Thus, the collection probe can be scanned around an illumination probe without destroying the probe tips. To demonstrate our SNOM, we performed photoluminescence spectroscopy under the dual-probe configuration and observed carrier motions in an InGaN quantum well.     

Spin-Probe Investigations of Head Group Behavior in Aqueous Dispersions of a Nonionic Amphiphilic Compound

Head group behavior of nonionic amphiphilic compound, (poly(oxyethylene) hydrogenated castor oil, HCO), in aqueous dispersions were investigated by EPR (electron paramagnetic resonance) in conjunction with a modern slow-tumbling simulation. The aliphatic spin probes, 5-doxylstearic acid (5-DSA) and 3β-doxyl-5α-cholestane (CHL), were used to obtain fluidity of the surface region of the membrane. The order parameter (S ₀) using the simulation for 5-DSA and CHL in the region were approximately 0.4 and 0.2, respectively. The ordering results suggest that the head group region of the membrane is somewhat fluid. The rotational diffusion coefficients (R _⊥ ≈ 1/(6τ_R)) for the probes were 3.4 × 10⁷ and 7.1 × 10⁷ s⁻¹, respectively. Activation energies, calculated using the temperature dependence of diffusion coefficients, were 18 and 17 kJ/mol for the probes. The EPR results imply that the CHL probe in the HCO membrane has quite different behavior in comparison with that of PC (phosphatidylcholine) from egg. Thus, the present EPR analyses have provided quantitative insight into the surface region of the amphiphilic membrane.     

Fe-4.2%Cr合金α/γ相变中相边界移动和晶粒长大的原位观察

In-situ observations on α/γ phase transformation were made to study the effects of grain boundary microstructures on the formation of a new phase and the migration of α/γ interphase boundary in an iron-4. 2%Cr alloy. It was found that triple junctions with more random boundaries could be the primary nucleation sites for a new phase, while triple junctions with low angle or low ∑ coincidence boundaries did not play any role as preferential sites. The migration of α/γ interphase boundary during heating over the transformation temperature range showed the two stage behaviour characterized by a stage with a migration velocity of 0. 33～0. 75 mm/s and secondly by a stage with 3. 7～7. 6 mm/s. It was also found that abnormal grain growth and a high density of ∑3 coincidence boundaries could occur in a phase with bcc structure after cycling of α/γ phase transformation. A new mechanism of nucleation and growth of a new phase in α/γ phase transformation is proposed on the basis of roles of plane-matching interphase boundaries, as previously discussed on the origin of anisotropy of grain growth due to the migration of {110} plane-matching boundaries in Fe-3%Si alloy. The most recent theoretical work on the distribution of plane-matching boundaries in solids with different crystal structures was found to be useful for the understanding of nucleation and growth during α/γ phase transformation.     

Fast acquisition system for digital holograms and image processing for three-dimensional display with data manipulation

A three-dimensional (3D) digital holographic display system with image processing is presented. By use of phase-shifting digital holography, we obtain the complex amplitude of a 3D object at a recording plane. Image processing techniques are introduced to improve the quality of the reconstructed 3D object or manipulate 3D objects for elimination and addition of information by modifying the complex amplitude. The results show that the information processing is effective in such manipulations of 3D objects. We also show a fast recording system of 3D objects based on phase-shifting digital holography for display with image processing. The acquisition of 3D object information at 500 Hz is demonstrated experimentally.