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991.
Kawaguchi M Okabe T Terai T Hanaoka K Kojima H Minegishi I Nagano T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(45):13479-13486
The prevalence of type 2 diabetes is increasing dramatically throughout the world. Recently, dipeptidyl peptidase 4 (DPP4) was identified as a potential antidiabetes target. Many DPP4 inhibitors, such as sitagliptin and vildagliptin, have been developed and marketed, but superior therapeutic agents are still required. Therefore, we have developed new methodology for screening of DPP4 inhibitors. Absorption-based measurements with para-nitroaniline or fluorescence-based measurements with the coumarin derivative 7-amino-4-methylcoumarin are often used for the screening of protease inhibitors, including DPP4 inhibitors, but these strategies are not sufficiently sensitive because of interfering background absorption and fluorescence, thus giving rise to many false-positive and false-negative results. Therefore, we have designed and synthesised a novel DPP4 probe (Gly-Pro-BCD-Tb; Gly=glycine, Pro=proline, andBCD defines the backbone of the probe comprising an aniline derivative as on/off switch, a 7-amino-4-methyl-2(1H)-quinolinone (cs-124) as antenna moiety, and a diethylenetriamine-N,N,N',N',N'-pentaacetic acid (DTPA) as chelator moiety, Tb=terbium) for time-resolved fluorescence (TRF) measurements. TRF measurements with Gly-Pro-BCD-Tb showed high sensitivity and reliability in the inhibitory assay relative to Gly-Pro-MCA (MCA=4-methylcoumarin-7-amide), a conventional fluorescence probe for DPP4. Further, we employed our probe for high-throughput DPP4 inhibitor screening with 3841 randomly selected compounds and found that epibestatin, an epimer of bestatin (a well-known anticancer drug and general aminopeptidase inhibitor), showed dose-dependent DPP4 inhibitory activity. Interestingly, bestatin did not exhibit DPP4 inhibitory activity. We believe that this screening system will be useful for the discovery of DPP4 inhibitors with novel structural scaffolds. 相似文献
992.
We present a model of photoinduced regular-dimerized stack transitions and discuss theoretically the behavior of the organic molecular mixed-stack charge-transfer crystal, Tetrathiafulvalene-Chloranil (TTF-CA). We investigate both the photoinduced structural phase transitions and the thermal phase transition between the regular-stack neutral phase at high temperatures and the dimerized-stack ionic phase at low temperatures. Our model is based on a simple phenomenological insight that the molecules have three stable displacements in the crystal. The cooperative effect is accounted for by introducing harmonic coupling between the molecules. It is the first attempt to include not only the photo-excitation but also the temperature effect on an equal footing. 相似文献
993.
Kuwabara T Shiba K Nakajima H Ozawa M Miyajima N Hosoda M Kuramoto N Suzuki Y 《The journal of physical chemistry. A》2006,110(50):13521-13529
Three modified beta-cyclodextrins appended with a hydroxyazobenzene as a dye unit, 1, 2, and 3, each incorporating a different length spacer between the beta-CD and the dye unit with a bis(propyl(oxyethylene)), butylene, and amide bond spacer, respectively, were synthesized in order to investigate their spectroscopic changes induced by pH and host-guest complexation as well as to investigate their conformations and guest-binding properties by means of absorption and induced circular dichroism spectroscopies in aqueous solutions. All hosts accommodated the dye unit in their own CD cavities with an orientation parallel to the CD axis, forming intramolecular complexes. When the pH of the solution changed, the structure changed in response to pH without conformational changes. Existing as the phenol form under acidic condition, they were converted to the yellow phenolate form by dissociation of a proton of the hydroxyl group in the dye unit with increasing pH (pK(a1); 7.62 for 1, 7.44 for 2, 8.00 for 3). Further increase in pH led to the dissociation of the ammonium proton in the secondary amine group in the spacer of 1 and 2 (pK(a2); 8.76 for 1, 8.67 for 2). Upon addition of 1-adamantanol (AN) as a guest, all hosts accommodated AN in their CD cavities, forming 1:1 host-guest inclusion complexes. The complexation phenomena were accompanied with changes in the conformation of the hosts, in which the dye units of 1 and 2 are excluded to outside of the cavity, but not for 3. The dye unit of 3 remained in the cavity, where the guest was also included partly. Therefore, the guest-binding abilities of 1 and 2 were larger than that of 3, which has poor binding ability. The binding constants of 1, 2, and 3 for AN are estimated to be 7400, 1940, and 140 M(-1) at pH 3.2, respectively. However, the guest-binding abilities of 1 and 2 were dependent on the pH of the solution. The ability of 1 under weak alkaline condition was stronger than under acidic or alkaline conditions, while that of 2 increased with increasing pH. Under the condition from neutral to weak alkaline media, 1 and 2 demonstrated color changes from colorless to yellow upon formation of inclusion complexes. When 1-adamantanecarboxylic acid (AC) was used as the charged guest, 1 and 2 bound to AC with a larger binding constant than AN. On the other hand, 1 and 2 bound to 1-adamantineamine (AA) with a smaller binding constant than AN. All these results demonstrate that the complexation phenomena depend on the pH of the solution as well as the length of the spacer of the hosts and that the electrostatic interaction between the host and the guest is also important for forming a stable complex. 相似文献
994.
Yamada H Kushibe K Okujuma T Uno H Ono N 《Chemical communications (Cambridge, England)》2006,(4):383-385
5-Alkenyl-15-alkynylporphyrins have been obtained unexpectedly by [2 + 2] acid-catalyzed condensation of dipyrrylmethane and TMS propynal in addition to 5,15-dialkynylporphyrin, and the unsymmetrical porphyrin can be converted to a butadiyne-linked dimer by selective desilylation of the alkynyl TMS. 相似文献
995.
Hoshino K Hirasawa Y Kim SK Saji T Katano J 《The journal of physical chemistry. B》2006,110(46):23321-23328
Photoelectrochemical cells based on oxotitanylphthalocyanine (TiOPc) films and an I(3)(-)/I(-) redox couple have been constructed. The TiOPc films were prepared on an indium-tin oxide coated glass plate (ITO) by the micellar disruption method and characterized by their unique nanoporous structure. A photocurrent action spectrum for input radiation directed through the ITO/TiOPc film, film-thickness dependence, and morphological investigation revealed that the cells consisted of a bulk heterojunction formed between the nanoporous TiOPc films and the liquid I3-/I- electrolyte, resulting in a larger short-circuit current (J(sc)= 2.1 mA/cm(2)), open-circuit voltage (V(oc)= 0.11 V), fill factor (ff= 0.31), and hence a larger energy conversion efficiency (eta= 0.13% for an incident white-light intensity of 53 mW/cm2) than the bilayer structure composed of the vaccum-evaporated TiOPc compact film and the I(3)(-)/I(-) electrolyte (J(sc)= 0.16 mA/cm(2), V(oc)= 0.018 V, ff = 0.27, and eta = (1.5 x 10(-3)%). 相似文献
996.
[reaction: see text] This research was undertaken to explore the interior surface of a synthetic receptor 1.1 with arylpyridines as guests. The interior surface differentiates the guests through the recognition of their nitrogen atoms. Experimental and computational analyses revealed that there is a delicate balance of attractions and repulsions between the host and the lone pairs of guests. 相似文献
997.
The purpose of the present study is to determine whether muscle functional MRI (mfMRI) can be used to obtain three-dimensional (3-D) images useful for evaluating muscle activity, and if so, to measure the distribution of muscle activity within a medial gastrocnemius (MG) muscle. Seven men performed 5 sets of 10 repetitions of a calf-raise exercise with additional 15% of body-weight load. Magnetic resonance images were obtained before and immediately after the exercise. To threshold images, only those pixels showing transverse relaxation time (T2) greater than the mean+1 S.D. of the entire regions of interest (ROIs) in the preexercise image and T2 lower than the mean+1 S.D. of the entire ROIs in the postexercise image were identified. The survived pixels showing T2 are defined as active muscle. Those thresholded images were 3-D reconstructed, and this was used to determine area of active muscle along transverse, longitudinal and vertical axes. At the exercise level used in the present study, the percentage volume of activated muscle in the MG was 62.8+/-4.5%. There was a significant correlation between percentage volume of activated muscle and integrated electromyography (r=.78, P<.05). Percentage areas of activated muscle were significantly larger in the medial than in the lateral region, in the anterior than in the posterior region and in the distal than in the proximal region (P<.05). These results suggest that mfMRI can be used to evaluate the muscle activity and to determine intramuscular variations of activity within skeletal muscle. 相似文献
998.
Kagiya G Ogawa R Tabuchi Y Feril LB Nozaki T Fukuda S Yamamoto K Kondo T 《Ultrasonics sonochemistry》2006,13(5):388-396
The present study was undertaken to elucidate the mechanism by which ultrasound induces the expression of heme oxygenase-1 (HO-1). When human lymphoma U937 cells were exposed to a 1 MHz continuous wave for 1 min, HO-1 expression examined by real-time quantitative polymerase chain reaction and immunoblotting was observed at intensities above the cavitational threshold. No induction of HO-1 expression was observed in the cells exposed for 1 min to 42 degrees C, a temperature higher than that during sonication. When a potent antioxidant, N-acetyl-l-cysteine, was added to the culture medium before or after sonication, the induction was attenuated, indicating that reactive oxygen species (ROS) are involved. However, the addition of catalase did not affect the induction, and no HO-1 was observed on the addition of pre-sonicated medium, suggesting that hydrogen peroxide due to the recombination of hydroxyl radicals generated extracellularly was not involved. The addition of free radical scavengers, glutathion-monoethyl ester, dimethyl sulfoxide and D(-)-mannitol, suppressed the induction. A decrease in mitochondrial membrane potential and the generation of superoxide were also observed in the sonicated cells, suggesting that mitochondria were the source of intracellularly generated ROS. These results indicate that superoxide secondarily generated from damaged mitochondria, not hydroxyl radicals generated in medium directly by sonication, give rise to intracellular oxidative stress inducing HO-1 expression. 相似文献
999.
Tetsuo Kuwabara Kazuyo Shiba Mayumi Ozawa Naoya Miyajima Yasutada Suzuki 《Tetrahedron letters》2006,47(26):4433-4436
Two β-cyclodextrin derivatives (1 and 2) bearing a hydroxyazobenzene unit, each having a butylene or a 4,7-dioxadecylene spacer between the cyclodextrin and the dye, were prepared, which showed guest-induced color changes with a marked difference in molecular recognition behavior in aqueous solution. 相似文献
1000.
Yasutaka Nakanishi Tetsuo Shibuya Akira Yasuhara 《Proceedings of the American Mathematical Society》2006,134(8):2465-2472
Self -equivalence is an equivalence relation for links, which is stronger than the link-homotopy defined by J. Milnor. It is known that cobordant links are link-homotopic and that they are not necessarily self -equivalent. In this paper, we will give a sufficient condition for cobordant links to be self -equivalent.