Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Analyses of the TCR repertoire of MHC class II-restricted innate CD4+ T cells

Analysis of the T-cell receptor (TCR) repertoire of innate CD4⁺ T cells selected by major histocompatibility complex (MHC) class II-dependent thymocyte–thymocyte (T-T) interaction (T-T CD4⁺ T cells) is essential for predicting the characteristics of the antigens that bind to these T cells and for distinguishing T-T CD4⁺ T cells from other types of innate T cells. Using the TCR^mini Tg mouse model, we show that the repertoire of TCRα chains in T-T CD4⁺ T cells was extremely diverse, in contrast to the repertoires previously described for other types of innate T cells. The TCRα chain sequences significantly overlapped between T-T CD4⁺ T cells and conventional CD4⁺ T cells in the thymus and spleen. However, the diversity of the TCRα repertoire of T-T CD4⁺ T cells seemed to be restricted compared with that of conventional CD4⁺ T cells. Interestingly, the frequency of the parental OT-II TCRα chains was significantly reduced in the process of T-T interaction. This diverse and shifted repertoire in T-T CD4⁺ T cells has biological relevance in terms of defense against diverse pathogens and a possible regulatory role during peripheral T-T interaction.     

Field-induced gelation, yield stress, and fragility of an electro-rheological suspension

 Electro-rheological suspensions (ERS) are known to undergo liquid-to-solid transition under the application of an electric field. Long-range interaction between neighboring particles results in sample-spanning particulate structures which behave as soft solids. Here, we studied the rheological expression of this field-induced transition which has many similarities with chemical gelation. This similarity shows in mechanical spectroscopy on a suspension of monodisperse silica in PDMS as model ERS. Upon application of the electric field, dynamic moduli G′, G′′ grow by orders of magnitude and evolve in a pattern which is otherwise typical for gelation of network polymers (random chemical or physical gelation). At the gel point, the slow dynamics is governed by power-law relaxation behavior (frequency-independent tan δ). A low field strength is sufficient to reach the gel point and, correspondingly, the percolating particle structure at the gel point is still very fragile. It can be broken by the imposition of low stress. For inducing a finite yield stress, the field strength needs to be increased further until the long-range electrostatic interaction generates string-like particle alignments which become clearly visible under the optical microscope. The onset of fragile connectivity was defined experimentally by the tan δ method. The ERS was probed dynamically at low frequencies where the transition is most pronounced, and also in steady shear where the rate of structure formation equals the rate of internal breaking. Received: 1 May 2001 Accepted: 11 August 2001     

Three-dimensional viscoelastic simulation of coextrusion process: comparison with experimental data

 Three-dimensional numerical simulation of viscoelastic coextrusion process has been performed and numerical results were compared with the experimental data of Karagiannis et al. (1990). By varying the magnitude of the second normal stress difference and its ratio of Fluid I and Fluid II, we were able to control the interface profile and the degree of encapsulation along the downstream direction. By increasing the parameter α (α_Fluid I=α_Fluid II) from 0.1 to 0.4 in the Giesekus model and increasing the α ratio (α_Fluid Iα_Fluid II) between Fluid I and Fluid II from 2.0 to 4.0 in the permissible range of realistic polymeric systems, the interface profile and the degree of encapsulation along the downstream direction were fitted with the experimental results. There was little difference between the numerical results and the experimental data in the interface profile and the degree of encapsulation along the downstream direction when the α ratio was set to 3.0 (0.3:0.1). Fluid I with larger magnitude of the second normal stress difference protrudes into Fluid II with smaller magnitude of the second normal stress difference around the symmetric plane, while Fluid II wraps around Fluid I near the side walls. As the ξ ₁ ratio (ξ _{1 ,Fluid I}ξ _{1 ,Fluid II}) increases from 1.0 to 3.0 for the two-mode Phan-Thien and Tanner model, it was found that the curvature of the interface profile increased, and the difference between the numerical results and the experimental data in the interface profile and the degree of encapsulation along the downstream direction was almost negligible when the ξ ₁ ratio was set to 3.0 (0.54:0.18). Although the parameters of viscoelastic models were fitted by using the shear viscosity data only, quantitative agreements between the numerical results and the experimental coextrusion data were quite satisfactory. Received: 24 April 2001 Accepted: 5 June 2001     

Development of simultaneous analysis of tryptophan metabolites in serum and gastric juice – an investigation towards establishing a biomarker test for gastric cancer diagnosis

To evaluate changes in tryptophan metabolism and discover diagnostic biomarkers for gastric cancer, a quantitative method was developed for tryptophan and its seven metabolites (indole‐3‐lactic acid, anthranilic acid, serotonin, nicotinic acid, kynurenic acid, kynurenine and 3‐indoxyl sulfate) in both human serum and gastric juice using liquid chromatography–tandem mass spectrometry (LC–MS/MS). Serum and gastric juice were prepared with a simple protein precipitation using aqueous 0.1% formic acid and acetonitrile. As a result, it was found that the kynurenine pathway of tryptophan metabolism was activated in gastric cancer and that the metabolic ratio of kynurenine/tryptophan, which reflects the enzyme activity of indoleamine‐2,3‐dioxygenase, was associated with the observed metabolic changes. Finally, the investigation of tryptophan metabolites, especially kynurenic acid, in serum and gastric juice might serve as biomarkers for gastric cancer. The findings in this study provide critical information of tryptophan metabolism which can be applied to a serum‐based diagnostic test for gastric cancer.     

The polyphenolic profiles and antioxidant effects of Agastache rugosa Kuntze (Banga) flower,leaf, stem and root

Agastache rugosa Kuntze (Korean mint) is used as a spice and in folk medicine in East Asia. The present study identified a total of 18 polyphenols from the flower, leaf, stem and roots of this plant using high‐performance liquid chromatography–tandem mass spectrometry. Fourteen of these compounds had not previously been identified in these plant tissues. Each polyphenol was validated in comparison with external calibration curves constructed using structurally related compounds, with determination coefficients >0.9993. The limits of detection and quantification were 0.092–0.650 and 0.307–2.167 mg/L, respectively. Recoveries of 61.92–116.44% were observed at two spiking levels, with 0.91–11% precision, expressed as relative standard deviation (except anthraquinone spiked at 10 mg/L). Hydroxycinnamic acid was the most abundant compound in the root, while the flowers showed the highest total flavonoid level. Antioxidant activities, determined in terms of reducing power, Fe²⁺ chelating activity and the radical scavenging activities using α,α‐diphenyl‐β‐picrylhydrazyl and 2‐2?‐azino‐bis‐3‐ethylbenzothiazoline‐6‐sulfonic acid, increased in a concentration‐dependent manner; the highest activity was identified in the stems, followed by leaves > flowers > roots. These findings indicate that A. rugosa is a good source of bioactive compounds and can be used as a functional food. Copyright © 2015 John Wiley & Sons, Ltd.     

Multichromophoric π‐Conjugation: Modular Design for Gated and Cascade Energy Transfer

Multichromophore arrays allow for cascade energy transfer. As an isoelectronic analogue of indacenyl, bis(triazolo)benzene features a fused tricyclic skeleton that rigidly places two π‐extended triazoles in close proximity. Such triazole‐based fluorophores behave as electronically independent modules in the ground states, but become tightly coupled upon photoexcitation for highly efficient excitation energy transfer (EET) that can be gated by external stimuli. Taking this donor–acceptor fluorophore system a step further, we have designed and implemented a cascade EET. Here, the initial excitation takes part in a circular relay to arrive at the longest‐wavelength emitting site as the final destination. Modularly constructed triazoloarenes should serve as versatile platforms for chemically controlled optical signaling.     

Controlling the spectrum of high-power terahertz radiation from a laser-driven plasma wave

Generation of strong THz waves is a very important and difficult research issue. We performed particle-in-cell (PIC) simulation studies to investigate the possibility of powerful THz generation and spectrum controllability by using a laser-driven plasma wave. Our results show that it is possible to produce spectrum-controllable high-power (>1 MV/cm) THz waves by manipulating the plasma density profiles. This method may provide a good way for coherent high-power THz radiation sources, of which the spectrum ranges from a narrow bandwidth to a wide bandwidth.