Calyciphyllines H-M, new Daphniphyllum alkaloids from Daphniphyllum calycinum

Six new Daphniphyllum alkaloids, calyciphyllines H-M (1-6), were isolated from the leaves and stems of Daphniphyllum calycinum (Daphniphyllaceae). The structures and relative stereochemistry of 1-6 were elucidated on the basis of spectroscopic data, and the absolute stereochemistry of 3 was assigned by PGME method.     

High-performance thin-layer chromatography/mass spectrometry for rapid analysis of neutral glycosphingolipids

Direct coupling of high-performance thin-layer chromatography (HPTLC) to matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometry (MS) was shown to be a reliable and reproducible method to obtain structural information and fundamental properties of glycosphingolipids (GSLs). We report a protocol for the preparation of neutral GSL extracts from mouse tissues and demonstrate the applicability of HPTLC/MS to these preparations. The protocol consists of lipid extraction and ion exchange chromatography followed by a mild alkaline treatment and a reversed-phase cartridge extraction. Possible structures for each GSL are proposed based on HPTLC/MS analyses. This fast and simple method can be used to screen neutral GSL extracts obtained from tissues and cells without isolation and purification into individual GSLs.     

All-solid-state high-peak-power Ti:sapphire laser system above 5-kHz repetition rate

We have developed an all-solid-state Ti:sapphire laser system, which produces 22-fs, 0.2-TW pulses at 5-kHz repetition rate. An average power of 22.2 W is the highest ever obtained in ultrashort laser sources. The serious thermal lensing due to high power pumping in a small area of Ti:sapphire crystal is controlled successfully by a stable quasi-cavity with two concave mirrors. The attempt to increase the repetition rate to 10 kHz is also described.     

Development of a fluorescent probe library enabling efficient screening of tumour-imaging probes based on discovery of biomarker enzymatic activities

Fluorescent probes that can selectively detect tumour lesions have great potential for fluorescence imaging-guided surgery. Here, we established a library-based approach for efficient screening of probes for tumour-selective imaging based on discovery of biomarker enzymes. We constructed a combinatorial fluorescent probe library for aminopeptidases and proteases, which is composed of 380 probes with various substrate moieties. Using this probe library, we performed lysate-based in vitro screening and/or direct imaging-based ex vivo screening of freshly resected clinical specimens from lung or gastric cancer patients, and found promising probes for tumour-selective visualization. Further, we identified two target enzymes as novel biomarker enzymes for discriminating between tumour and non-tumour tissues. This library-based approach is expected to be an efficient tool to develop tumour-imaging probes and to discover new biomarker enzyme activities for various tumours and other diseases.

Efficient methodology to develop tumor-imaging fluorescent probes based on screening with our newly constructed probe library for aminopeptidase/protease (380 probes) and clinical samples has been established.     

Enhancing effect of pyrrolidone derivatives on transdermal penetration of phenolsulfonphthalein and indomethacin from aqueous vehicle

We investigated the enhancing effect of three alkyl-2-pyrrolidones on transdermal penetration of phenolsulfonphthalein (phenol red) and indomethacin from an aqueous vehicle by using an in vitro technique with excised rat skin. The enhancers included 1-methyl- (I), 1-hexyl- (II) and 1-lauryl-2-pyrrolidone (III). These derivatives effectively enhanced the penetration and skin accumulation of phenol red and indomethacin. Lipophilic enhancers such as II and III showed particularly high enhancing effects. The penetration profiles of phenol red and indomethacin showed a lag phase followed by a linear increase. Compounds II and III showed long lag times. The enhancer penetration was also determined. Compounds I and II showed a slight penetration. Compound III showed little penetration but high skin accumulation.     

Discretization and localization in successive convex relaxation methods for nonconvex quadratic optimization

Based on the authors’ previous work which established theoretical foundations of two, conceptual, successive convex relaxation methods, i.e., the SSDP (Successive Semidefinite Programming) Relaxation Method and the SSILP (Successive Semi-Infinite Linear Programming) Relaxation Method, this paper proposes their implementable variants for general quadratic optimization problems. These problems have a linear objective function c ^T x to be maximized over a nonconvex compact feasible region F described by a finite number of quadratic inequalities. We introduce two new techniques, “discretization” and “localization,” into the SSDP and SSILP Relaxation Methods. The discretization technique makes it possible to approximate an infinite number of semi-infinite SDPs (or semi-infinite LPs) which appeared at each iteration of the original methods by a finite number of standard SDPs (or standard LPs) with a finite number of linear inequality constraints. We establish:?•Given any open convex set U containing F, there is an implementable discretization of the SSDP (or SSILP) Relaxation Method which generates a compact convex set C such that F⊆C⊆U in a finite number of iterations.?The localization technique is for the cases where we are only interested in upper bounds on the optimal objective value (for a fixed objective function vector c) but not in a global approximation of the convex hull of F. This technique allows us to generate a convex relaxation of F that is accurate only in certain directions in a neighborhood of the objective direction c. This cuts off redundant work to make the convex relaxation accurate in unnecessary directions. We establish:?•Given any positive number ε, there is an implementable localization-discretization of the SSDP (or SSILP) Relaxation Method which generates an upper bound of the objective value within ε of its maximum in a finite number of iterations. Received: June 30, 1998 / Accepted: May 18, 2000?Published online September 20, 2000     

DDSC Studies on POTMG/PMMA Blends and POTMDM-net-PMMA

Thermal behaviors of POTMDM-net-PMMA and POTMG/PMMA blends were studied by DDSC. T_g of the polymer network was lowered by increasing the POTMDM in feed for copolymerization of POTMDM and MMA. A crystallization peak was observed only when MMA in feed was less than 30%. T_g of POTMG/PMMA was also lowered by decreasing the content of PMMA, however, the change was observed only when PMMA content was more than 70%. These results suggest that thermal transitions of the polymer network are restricted by the mesh size. POTM chains of the polymer network effectively play as a plasticiser. This revised version was published online in August 2006 with corrections to the Cover Date.