Association and physical gelation of ABA triblock copolymer in selective solvent

Association behavior and physical gelation mechanism of ABA triblock copolymer dissolved in B-selective solvent have been studied systematically from dilute to moderately concentrated solutions. Static and dynamic light scattering and nuclear magnetic resonance measurements for dilute solutions of poly(methyl methacrylate)-block-poly(tert-butyl acrylate)-block-poly(methyl methacrylate) (PMMA-PtBuA-PMMA) in 1-butanol (PtBuA selective solvent) indicated that PMMA-PtBuA-PMMA chains are molecularly dissolved above 50 °C. With decreasing temperature, the triblock copolymers form associated micelles consisting PMMA associated core and PtBuA shell. Linear dynamic viscoelastic measurements for solutions with moderate concentration (3.9-12.0 wt%) revealed that the system was viscous sol state at 60 °C. Drastic increase of shear storage modulus (G′) occurred with decreasing temperature, and at 25 °C, G′ showed rubbery plateau with weak frequency dependency, means the formation of elastic physical gel. The consistency between the temperature for micelle formation and that at the increase in G′ indicates that the physical gelation is owing to the network formation as the result of the association of PMMA chains and the bridging PtBuA chains connecting the PMMA cores. Master curves for the dynamic moduli were derived by time-temperature superposition along the frequency axis. Just above sol-gel transition concentration (C_gel), the master curves suggest the existence of fairy amount of aggregate that is not incorporated in the macroscopic network. With the increase in polymer concentration, the master curves become to reveal Maxwell-type viscoelasticity with narrow relaxation time distribution, suggesting the formation of transient network with easily generation and destruction of crosslinks. Concentration dependency of the plateau modulus is stronger than the theoretically expected, means the macroscopic transient network grows with polymer concentration by increasing the fraction of elastically effective bridging PtBuA chain above C_gel.     

Fritless packed columns for capillary electrochromatography: separation of uncharged compounds on hydrophobic hydrogels

A novel column is described that does not require frits to keep packing material within a capillary. A continuous bed is prepared in situ in aqueous solution by radical copolymerization of N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid (the resultant gel is denoted poly(AMPS-co-IPAAm). N,N'-Methylenebisacrylamide is used for cross-linking. On the application of an electrical field, electroosmotic flow (EOF) is developed in the bed along the capillary, where fluid propulsion would be otherwise difficult to achieve. The resultant EOF transports neutral compounds through the column without forcing the gel out of the capillary. Examination of the fluid motion in the continuous bed using a video microscope system and an image processor shows a relatively flat flow profile of EOF. The bed functions as the stationary phase for reversed-phase capillary electrochromatography (CEC). This new approach is an alternative to packed capillary columns which have been used previously in CEC. A high efficiency is obtained for a steroid which is separated on a 4.0% total monomer concentration (T), 10.0% degree of cross-linking (C), and 10.0% mole fraction of AMPS in the total monomer (S), poly(AMPS-co-IPAAm) column. A mixture of polyaromatic hydrocarbons is separated on a 6.9% T, 5.8% C, and 5.5% S poly(AMPS-co-IPAAm) column. The capacity factor of benzo[a]pyrene increases from 0.63 to 1.91 as the acetonitrile content in a Tris-boric acid buffer is decreased from 45 to 30% (v/v). The run-to-run RSD of analyte migration time is less than 0.73%, and the day-to-day RSD is acceptable. Potential benefits of this approach are also mentioned.     

The effect of lutein supplementation on visual fatigue: A psychophysiological analysis

We used psychophysiological technology to examine the effect of an oral supplement, a combination of lutein, zeaxanthin and blackcurrant extract (LUT), on visual fatigue, within the context of a randomized, double-blind, placebo-controlled cross-over trial. The LUT supplement and placebo samples were randomly assigned to thirteen participants, who took the samples for two LUT (and vice versa) for another 2 week. Each participant completed visual proof reading tasks for 2 h during each of four testing sessions. Saccade tests were administered before and after the proof reading task, during which the participants moved their eyes back and forth between two targets positioned in the center of two checkerboards. We recorded EEG, EOG, heart rate, and facial muscle potential/performance during the saccade tests. Blood pressure was measured and subjective fatigue and stress scores were collected before and after the proof reading task. We averaged EEG starting at saccade offset in order to analyze eye fixation related potentials (EFRP). Our results suggested that the proof reading task induced visual fatigue. An analysis of EFRP and other psychophysiological data revealed significant differences between the LUT and placebo conditions. These results suggest that supplementation with LUT could help to reduce symptoms of visual fatigue.     

Magnetic probe array with high sensitivity for fluctuating field

A magnetic probe array is constructed to measure precisely the spatial structure of a small fluctuating field included in a strong confinement field that varies with time. To exclude the effect of the confinement field, the magnetic probes consisting of figure-eight-wound coils are prepared. The spatial structure of the fluctuating field is obtained from a Fourier analysis of the probe signal. It is found that the probe array is more sensitive to the fluctuating field with a high mode number than that with a low mode number. An experimental demonstration of the present method is attempted using a field-reversed configuration plasma, where the fluctuating field with 0.1% of the confinement field is successfully detected.     

Dynamic alternation of primate response properties during trial-and-error knowledge updating

Humans and animals seek appropriate solutions to novel problems through trial-and-error (TE) actions and observation of their outcomes. Once an individual has obtained the knowledge (rule) to solve a problem, knowledge-based (KB) actions may be applied in a stereotypical manner. Solutions can thus be based on TE or KB actions. To characterize this learning process at the behavioral level, we developed a new cognitive task for a laboratory monkey (Macaca fuscata) to perform. In this task, a search array consisting of six elements of different colors was presented, one of which was the behaviorally relevant target. The target color was changed unpredictably with no instruction or signal, requiring the monkey to use a TE search strategy to find the target color. We found that once the monkey identified the relevant color by chance after a color change, correct performance increased in a step-like manner and at the same time, other response properties (reaction time and color-choice tendency) also changed discontinuously. These step-like alternations in behavioral performance may be attributed to the subject’s switching between TE and KB search strategies in the two phases. The present study has therefore provided behavioral evidence for the timing and manner of switching between search strategies during the process of updating knowledge.     

Electrochemical behaviour of pyridinoline, a crosslinking amino acid of collagen

Pyridinoline is a crosslinking amino acid isolated from collagen. Polarographic oxidation and reduction potentials of pyridinoline were measured and compared with those of structurally related compounds, 3-hydroxypyridine, pyridoxine, pyridoxal, and N-methylpyridoxine. Oxidation and reduction potentials of these compounds were found to be near anodic and cathodic limit potentials, respectively, except for pyridoxal. This indicates that a 3-hydroxypyridine ring is very difficult to be reduced or oxidized. The reducibility of pyridinoline with a reducing agent, sodium borohydride, was also studied. It was not reduced by the reagent, however, it was found to be decomposed by light during the treatment. These results indicate that pyridinoline is a so-called "non-reducible" crosslink.     

An integrated procedure for three‐dimensional structural analysis with the finite cover method

In this paper an integrated procedure for three‐dimensional (3D) structural analyses with the finite cover method (FCM) is introduced. In the pre‐process of this procedure, the geometry of a structure is modelled by 3D‐CAD, followed by digitization to have the corresponding voxel model, and then the structure is covered by a union of mathematical covers, namely a mathematical mesh independently generated for approximation purposes. Since the mesh topology in the FCM does not need to conform to the physical boundaries of the structure, the mesh can be regular and structured. Thus, the numerical analysis procedure is free from the difficulties mesh generation typically poses and, in this sense, enables us to realize the mesh‐free analysis. After formulating the FCM with interface elements for the static equilibrium state of a structure, we detail the procedure of the finite cover modelling, including the geometry modelling with 3D‐CAD and the identification of the geometry covered by a regular mesh for numerical integration. Prior to full 3D modelling and analysis, we present a simple numerical example to confirm the equivalence of the performance of the FCM and that of the standard finite element method (FEM). Finally, representative numerical examples are presented to demonstrate the capabilities of the proposed analysis procedure. Copyright © 2005 John Wiley & Sons, Ltd.     

Iterative learning control of Hamiltonian systems: I/O based optimal control approach

In this note, a novel iterative learning control scheme for a class of Hamiltonian control systems is proposed, which is applicable to electromechanical systems. The proposed method has the following distinguished features. This method does not require either the precise knowledge of the model of the target system or the time derivatives of the output signals. Despite the lack of information, the tracking error monotonously decreases in L/sub 2/ sense and, further, perfect tracking is achieved when it is applied to mechanical systems. The self-adjoint related properties of Hamiltonian systems proven in this note play the key role in this learning control. Those properties are also useful for general optimal control. Furthermore, experiments of a robot manipulator demonstrate the effectiveness of the proposed method.     

Current dependence of performance of TES microcalorimeters and characteristics of excess noise

We are developing transition edge sensor (TES) microcalorimeter arrays for future Japanese astronomy missions. Although 6.6 eV energy resolution for 5.9 keV and 74 μs decay time are achieved, our energy resolution was limited by the excess noise of unknown origin. The dominant noise showed 1/R dependence and it only appeared when the current through the TES, I, is larger than 10 μA. This is explained if we assume a constant voltage noise source with a level of 2(4kT_CR_n)^1/2. We also investigated the influence of I on the TES performance and found the TES sensitivity is reduced when the ratio of current to the critical current I/I_C is large. It can explain the reduction of observed when operated without a magnetic shield. We also found a strong correlation between I_C and or the baseline width. Thus, we conclude that I_C is an essential parameter for the TES performance.