Chiral sensing system based on the formation of diastereomeric metal complex on a homocysteine monolayer using field effect transistor

A self-assembled monolayer (SAM) of l-homocysteine (l-Hcy) formed on the surface of a gold-deposited gate of a field effect transistor (FET) was used to differentiate between enantiomers of amino acids, for which the formation of diastereomeric metal complexes is fundamental for chiral discrimination. Here, we focus our attention on the dependence of the FET response on the analyte amino acids, the central metal ions involved in complex formation, and the solution pH. Using the l-Hcy SAM-modified gate with added Cu(II), notable negative FET responses were enantioselectively observed for the l-enantiomers of alanine (Ala), phenylalanine, and tryptophan, whereas differences in the FET responses between enantiomers were negligible for asparagine and aspartic acid. Regarding the enantioselectivity for Ala, the addition of Cu(II) was demonstrated to show higher selectivity as compared to other metal ions such as Co(II) and Ni(II). Moreover, for the addition of l-Ala and Cu(II), a particularly strong negative FET response was observed at pH 5.5.     

Double layer capacitance of high surface area carbon nanospheres derived from resorcinol–formaldehyde polymers

Micro-mesoporous bimodal carbon nanospheres with high surface areas were synthesized by a combined use of surfactant templating technique and BaO₂ chemical activation one. Starting spherical nanopolymer/surfactant composites were prepared by the NaOH-catalyzed reaction of resorcinol (R) and formaldehyde (F) in the presence of cetyltrimethylammonium bromide (CTAB) as a core template and 1,3,5-trimethylbenzene (TMB) and tert-butanol (t-BuOH) as cosurfactants. After pretreatment with hydrochloric acid, the composite materials were calcined at 1000 °C in N₂ coexistent with varying weight ratios of BaO₂ to RF polymer ranging from 0 to 11. It produced micro-mesoporous bimodal carbon nanospheres of 124–143 nm diameter, with specific surface areas as high as 1884 m² g⁻¹ or up to 3301 m² g⁻¹, in contrast to microporous ones with smaller surface areas obtained at low BaO₂-loadings. The electrochemical double layer capacitance of the resulting nanocarbons in 0.5 M H₂SO₄ showed a marked increase with specific surface areas, up to as high as 219 F g⁻¹ for the highest surface area carbon material.     

Enzymatic Synthesis of 1‐Alkyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate Using a Novel Lysoplasmalogen‐Specific Phopholipase D

Many phospholipase Ds (PLDs) are known to catalyze transphosphatidylation as well as hydrolysis of phospholipids. Transphosphatidylation of lysoplasmalogen (LyPls)‐specific phospholipase D (LyPls‐PLD), which catalyzes hydrolysis of ether lysophospholipids such as LyPls and 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine (Lyso‐PAF), still remains unclear. This study aims to reveal the transphosphatidylation activity of LyPls‐PLD, that is, the production of cyclic ether lysophospholipid. The enzymatic reaction is conducted in a buffer system, and the reaction products of a novel LyPls‐PLD from Thermocrispum sp. are investigated using mass spectrometry (MS). MS analyses demonstrate the reaction products to consist of 100% 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate (cLyPA) and choline from Lyso‐PAF; however, 1‐alkenyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate from 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine and 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphoethanolamine is not produced. These results are expected to help in elucidating the catalytic mechanism of LyPls‐PLD, that is, the rate‐limiting step, and indicate LyPls‐PLD to be useful for the one‐pot synthesis of cLyPA. Practical Applications: A novel phospholipase D, LyPls‐PLD, can exclusively synthesize cLyPA from Lyso‐PAF using a one‐step enzymatic reaction without an organic solvent. cLyPA could be expected to show bioactivities similar to those of cyclic phosphatidic acid, which promotes normal cell differentiation, hyaluronic acid synthesis, antiproliferative activity in fibroblasts, and inhibitory activity toward cancer cell invasion and metastasis.     

Light scattering studies on crystallization in polyethylene terephthalate

The light scattering from the spherulites of polyethylene terephthalate grown near the glass transition temperature has been investigated. The Hv scattering profiles can be reproduced by the sum of the ideal spherulite scattering with the distribution of spherulite radius and the isotropic scattering from randomly oriented crystallites. The ratio of optical anisotropies in the isotropic scattering to the ideal spherulite scattering is obtained by the method established to eliminate the effects of the number density of spherulites and the coefficient depending on the experimental conditions. It is found that the anisotropy ratio is almost independent of the crystallization time and of temperature above 106 °C, while it is larger at a crystallization temperature of 103 °C. The spherulitic structure is discussed in terms of the anisotropy ratio.     

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.     

Tensile fatigue of a laminated carbon-carbon composite at room temperature

The tensile fatigue behavior of a cross-ply carbon-carbon (C/C) laminate was examined at room temperature. Tension-tension cyclic fatigue tests were conducted under load control at a sinusoidal frequency of 10 Hz to obtain stress-fracture cycles (S-N) relationship. The fatigue limit of the C/C was found to be 213 MPa (93% of the tensile strength), and no fracture was observed at over 10⁴ cycles. The residual tensile strength of specimens that survived fatigue loading was enhanced with increase in fatigue cycles and applied stress. Observations of the fatigue-loaded specimens revealed that the formation of micro-cracks at the fiber-matrix interfaces was facilitated during fatigue loading. These interfacial cracks were concluded to protect the fibers from being damaged by matrix cracks and this behavior was considered to be the governing mechanism of strength enhancement by fatigue loading.     

Increased Lipid Synthesis and Decreased β-Oxidation in the Liver of SHR/NDmcr-cp (cp/cp) Rats, an Animal Model of Metabolic Syndrome

SHR/NDmcr-cp (cp/cp) rats (SHR/NDcp) are an animal model of metabolic syndrome. A previous study of ours revealed drastic increases in the mass of palmitic (16:0), oleic (18:1n-9), palmitoleic (16:1n-7), cis-vaccenic (18:1n-7) and 5,8,11-eicosatrienoic acids in the liver of SHR/NDcp. However, detailed information on the class of lipid accumulated and the mechanism responsible for the overproduction of the accumulated lipid in the liver was not obtained. This study aimed to characterize the class of lipid accumulated and to explore the mechanism underlying the lipid accumulation in the liver of SHR/NDcp, in comparison with SHR/NDmcr-cp (+/+) (lean hypertensive littermates of SHR/NDcp) and Wistar Kyoto rats. In the liver of SHR/NDcp, de novo synthesis of fatty acids (16:0, 18:1n-9 and 16:1n-7) and triacylglycerol (TAG) synthesis were up-regulated and fatty acid β-oxidation was down-regulated. These perturbations of lipid metabolism caused fat accumulation in hepatocytes and accumulation of TAG, which were enriched with 16:0, 18:1n-9 and 16:1n-7, in the liver of SHR/NDcp. On the other hand, no changes were found in hepatic contents of diacylglycerol and unesterified fatty acid (FFA); among FFA, there were no differences in the hepatic concentrations of unesterified 16:0 and stearic acid between SHR/NDcp and two other groups of rats. Moreover, little change was brought about in the expression of genes responsive to endoplasmic reticulum stress in the liver of SHR/NDcp. These results may reinforce the pathophysiological role of stearoyl-CoA desaturase 1 and fatty acid elongase 6 in the liver of SHR/NDcp.     

Candidate Biomarkers for Genetic and Clinicopathological Diagnosis of Endometrial Cancer

The recent increase in the frequency of endometrial cancer has emphasized the need for accurate diagnosis and improved treatment. The current diagnosis is still based on conventional pathological indicators, such as clinical stage, tumor differentiation, invasion depth and vascular invasion. However, the genetic mechanisms underlying endometrial cancer have gradually been determined, due to developments in molecular biology, leading to the possibility of new methods of diagnosis and treatment planning. New candidate biomarkers for endometrial cancer include those for molecular epigenetic mutations, such as microRNAs. These biomarkers may permit earlier detection of endometrial cancer and prediction of outcomes and are likely to contribute to future personalized therapy for endometrial cancer.