Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Stable all-optical formation of Bose–Einstein condensate using pointing-stabilized optical trapping beams

By stabilizing the beam pointing of optical trapping beams, we have succeeded in stable formation of Bose–Einstein condensate (BEC) of ⁸⁷Rb with all-optical method. The thermal effect of acousto-optic modulator (AOM) is usually one of the most serious problems to induce beam-pointing instability, especially for high power CO₂ laser. By passing the beam through AOM twice, we have improved the beam pointing from about 4.8 mrad to less than 0.4 mrad, which has been experimentally confirmed to be small enough to stably form BEC at the crossed region of CO₂ lasers as well as to perform experiments using an optical lattice which might have been affected by beam-pointing instability. PACS 32.80.Pj; 42.79.Jq; 03.75.Mn     

Long-wavelength light emission from InAs quantum dots covered by GaAsSb grown on GaAs substrates

We fabricated InAs quantum dots (QDs) with a GaAsSb strain-reducing layer (SRL) on a GaAs(0 0 1) substrate. The wavelength of emission from InAs QD is shown to be controllable by changing the composition and thickness of the SRL. An increase in photoluminescence intensity with increasing compositions of Sb and thickness of the GaAsSb SRL is also seen. The efficiency of radiative recombination was improved under both conditions because the InAs/GaAsSb/GaAs hetero-interface band structure more effectively suppressed carrier escape from the InAs QDs.     

A new luciferase reporter gene assay for the detection of androgenic and antiandrogenic effects based on a human prostate specific antigen promoter and PC3/AR human prostate cancer cells.

We developed a new mammalian cell-based luciferase reporter gene assay for androgenic and antiandrogenic activities of chemicals and environmental samples. Environmental samples usually have a complex matrix that may contain the constituents acting as androgen receptor (AR) agonists, AR antagonists or aryl hydrocarbon receptor (AhR) agonists. AhR agonists are known to elicit the antiandrogenic effect through cross-talk between AR and AhR signal transduction pathways. In this study, PC3/AR human prostate carcinoma cells were transiently transfected with a prostate-specific antigen (PSA) promoter-driven luciferase expression plasmid. The cells were treated with a test compound or an environmental sample for 24 h at 37 degrees C and then measured for luciferase activity. The luciferase activity was induced by dihydrotestosterone (DHT) in a concentration-dependent manner in a concentration range from 10 fM to 1 nM. R1881, a synthetic androgen receptor agonist, induced luciferase activity and its inductive effects was additive to that of DHT. The luciferase activity was not induced by cortisol, a glucocorticoid, progesterone, a progestin, and 17beta-estradiol, an estrogen in a concentration range of up to 1 microM. DHT-induced luciferase activity was reduced by bicalutamide and cyproterone acetate, AR antagonists, and also by benzo[a]pyrene, an aryl hydrocarbon receptor agonist, through AhR-mediated pathways. All of these findings indicate that the present assay system correctly responds to AR agonists, AR antagonists and AhR agonist and, therefore, it is a powerful tool for the sensitive and selective screening of chemicals and environmental samples for their androgenic and antiandrogenic activities. We developed the first assay system, in which the expression of luciferase was driven by the promoter of a prostate-specific antigen gene, a typical human androgen-regulated gene.     

Boundary position feedback control of Kirchhoff's non‐linear strings

This paper is concerned with global stabilization of an undamped non‐linear string in the case where any velocity feedback is not available. The linearized system has an infinite number of poles and zeros on the imaginary axis. In the case where any velocity feedback is not available, a parallel compensator is effective. The stabilizer is constructed for the augmented system which consists of the controlled system and a parallel compensator. It is proved that the string can be stabilized by linear boundary control. Copyright © 2003 John Wiley & Sons, Ltd.     

Constructing finitely presented monoids which have no finite complete presentation

Squier (1987) showed that if a monoid is defined by a finite complete rewriting system, then it satisfies the homological finiteness condition FP₃, and using this fact he gave monoids (groups) which have solvable word problems but cannot be presented by finite complete systems. In the present paper we show that a monoid cannot have a finite complete presentation if it contains certain special elements. This observation enables us to construct monoids without finite complete presentation in a direct and elementary way. We give a finitely presented monoid which has (1) a word problem solvable in linear time and (2) linear growth but (3) no finite complete presentation. We also give a finitely presented monoid which has (1) a word problem solvable in linear time, (2) finite derivation type in the sense of Squier and (3) the property FP_∞, but (4) no finite complete presentation.     

Communication network protocol for real-time distributed controland its LSI implementation

A new token-passing mechanism, priority token passing, which features real-time access and fast detection and recovery of transmission errors, is discussed in detail in comparison with standard token-passing protocols, and its large-scale integration (LSI)-oriented design concept is described. Priority token passing includes only a small performance overhead, due to its switching functions, which can change network topology from ring to broadcast medium. A token-holding node passes the token to another node after determining the successor through priority comparison. Errors occurring during token passing can, thus, be detected and corrected simply and promptly. Priority token passing has a simple hardware implementation, requiring only small additions to the frame control circuitry, and has a small implementation overhead. The priority token-passing protocol and two other important network communication functions, dual ring network reconfiguration and high-level data link control (HDLC) normal response mode-based message transmission, are designed as a single finite-state machine, and implemented into a compact LSI chip. This integrated instrument network (IINET) chip provides complete network communication services and requires only three additional external electronic components for operation     

Phase and amplitude comparison between experiment and calculation of ultrabroad-band pulses generated in a taper fiber

Using a cross-correlation frequency-resolved optical gating apparatus, the phases and amplitudes of ultrabroad-band optical pulses from a taper fiber have been measured for various input pulse peak powers. The measured waveforms have been compared with calculated waveforms using a finite-difference in the frequency domain method, in which no envelope approximations were used and the variation of the taper shape was taken into account. Excellent agreement between the measured and the calculated waveforms was obtained when the additional dispersion of a normal fiber and an objective was considered.     

Numerical reconstruction of an infrared wavefront utilizing an optical phase modulation device

We utilize nitroanisole, that absorbs infrared (IR) radiation as heat, as an optical modulation device based on a thermal process. The nitroanisole exhibits a thermal lens effect, i.e. a temperature dependent refractive index. Hence, the nitroanisole can induce phase modulation to visible light, in direct response to intensity of the incident IR radiation. The proposed method can be used to obtain the phase modulation distribution that corresponds to the IR intensity distribution, i.e. the IR hologram itself, on the nitroanisole by examining the phase map of visible light that is modulated upon passing through the nitroanisole. The IR wavefront can be reconstructed by calculating extracted IR holograms through the Fresnel transform. It is verified that both the amplitude and the phase of the IR wavefront can be reconstructed accurately by proposed method.