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991.
Many experimental results have been reported which demonstrated deviation of the apparent lightness from the calculated lightness based on spectral reflectance, and these have caused debate among researchers as to the models to explain them. The judgement of lightness of objects that we see in the outside world is one of the most important tasks in our daily life. We proposed the recognized visual space of illumination, RVSI, as a three dimensional recognition constructed in the brain for the outside world, and showed that the apparent lightness was determined in relation to the size of the RVSI. In the present paper the concept was applied to various results of lightness experiments such as the White effect and simultaneous contrast, and based on the proposition that an observer first builds a three dimensional RVSI from a two dimensional pattern and the lightness of a test patch was judged in relation to the size of this RVSI, the results were then globally and nicely explained. A new demonstration of a pattern was proposed to give different apparent lightness for patches with the same physical lightness to strengthen the proposition. The importance of distinguishing between a test patch and a surrounding field was emphasized when one does a lightness experiment and interprets the results. 相似文献
992.
Nagaki A Kawamura K Suga S Ando T Sawamoto M Yoshida J 《Journal of the American Chemical Society》2004,126(45):14702-14703
The "cation pool" of an N-acyliminium ion was found to serve as an effective initiator of cationic polymerization of vinyl ethers in a microsystem consisting of two micromixers and a microtube reactor. The polymerization led to very narrow molecular weight distribution (Mw/Mn = 1.14). The molecular weight (Mn) increased linearly with an increase in the amount of the monomer. The carbocationic polymer end was effectively trapped by allyltrimethylsilane. The present observations illustrate the potential of microsystems, in conjunction with the cation pool, to effect polymerization in a highly controlled manner without the deceleration inherent in the dynamic equilibrium between active and dormant species. 相似文献
993.
Sekine M Okada K Seio K Kakeya H Osada H Obata T Sasaki T 《The Journal of organic chemistry》2004,69(2):314-326
Phosmidosine is known to have potent antitumor activity and the unique property of stopping cell growth at the G(1) phase in the cell cycle. However, this natural product having N-prolylphosphoramidate and O-methyl ester linkages on the 5'-phosphoryl residue is unstable under basic conditions and even during the chemical synthesis due to its inherent methyl transfer activity. To find stable derivatives of phosmidosine, a variety of phosmidosine analogues 1a-d replaced by longer alkyl groups in place of the methyl group on the phosphoramidate linkage were synthesized by reaction of alkyl N-(N-tritylprolyl)phosphorodiamidite derivatives 7a-d with an 8-oxoadenosine derivative 4 protected with acid-labile protecting groups. Consequently, the O-ethyl ester derivative 1b was found to be sufficiently stable in aqueous solution. When the prolyl group was replaced by other aminoacyl moieties, the reaction of N-tritylaminoacylamide derivatives 25a-d with an appropriately protected 8-oxoadenosine 5'-(ethyl phosphoramidite) derivative 9 gave better results than the above coupling reaction. A phosphoramidothioate derivative 17 and several simple compounds such as 11, 13, and 15 lacking partial structures of phosmidosine were also synthesized. The antitumor activities of these modified analogues were extensively studied to clarify the structure-activity relationship of phosmidosine. As a result, the two diastereoisomers of longer alkyl-containing phosmidosine analogues both proved to have similar antitumor activities. Replacement of l-proline with other l-amino acids or d-proline resulted in considerable decrease of the antitumor activity. The non-nucleotidic materials 13 did not show any antitumor activity, but a simple core compound of 11 exhibited weak cytotoxicity. The phosphoramidothioate derivative 17 maintained essentially a similar antitumor activity, but the efficiency decreased slightly. 相似文献
994.
Kohji Seio Takeshi Terada Masahiro Mizuta Akihiro Ohkubo Haruhiko Taguchi Mitsuo Sekine 《Helvetica chimica acta》2007,90(10):1946-1965
New oligonucleotides with a long‐chain linker (6,9‐dioxa‐3,12‐diazatetradecane‐1,14‐diyl) in their backbone were synthesized, and their hybridization properties were studied by measurement of their Tm curves and fluorescence spectra. The Tm analyses revealed that these oligonucleotides could bind to their complementary strands despite the presence of the long‐chain linker. We also demonstrated interesting fluorescence properties of oligodeoxynucleotides with an anthracen‐9‐ylmethyl group on one of the two N‐atoms in the long‐chain linker. The fluorescence intensity of these oligonucleotides increased upon their hybridization to the complementary strands and was sensitive to the presence of the mismatch base pairs at a specific position. 相似文献
995.
M Mitsukuchi T Ikemoto M Taguchi S Higuchi S Abe H Yasui K Hatayama K Sota 《Chemical & pharmaceutical bulletin》1989,37(12):3286-3293
A series of 21-thio derivatives of 9 alpha-fluoro-11 beta,17 alpha-dihydroxy-16 beta-methyl-1,4-pregnadiene-3, 20-dione 17-esters and related compounds were synthesized and evaluated as topical antiinflammatory agents. These compounds were prepared by the reaction of 9 alpha-fluoro-11 beta,17 alpha,21-trihydroxy-16 beta-methyl-1,4-pregnadiene-3, 20-dione (betamethasone, I) 17-ester derivatives and various mercapto compounds. A structure-activity relationship study revealed that the structural combination of a thio group at the 21-position and an ester group at the 17-position contributed to vasoconstrictive activity. Among these compounds, the 21-methylthio 17-propanoate compound (6) was found to have the most potent activity, being more potent than betamethasone 17-valerate (BV). 相似文献
996.
The new protecting groups 1a , b and 2a , b were developed for the 5′‐OH group of deoxynucleosides by utilizing the unique characters of the sulfenate and sulfenamide linkage. These new protecting groups have a 2‐(hydroxymethyl)benzoyl or 2‐[(methylamino)methyl]benzoyl skeleton whose hydroxy O‐atom or amino N‐atom was blocked with a tritylthio‐type substituent. They are removable by intramolecular cyclization following the oxidative hydrolysis of the tritylthio‐type substituents under mildly oxidative conditions (Schemes 3 and 6). Among them, 2‐{{[(4‐methoxytrityl)sulfenyl]oxy}methyl}benzoyl (MOB; 2b ) was found to be the most preferable for protection of the 5′‐OH function of deoxynucleosides. MOB can be introduced at the 5′‐OH groups of various deoxynucleosides without the protection of the 3′‐OH functions (Scheme 5). The applicability of the MOB group to a new oligodeoxynucleotide synthesis protocol without acid treatment was demonstrated by the solid‐phase synthesis of a tetrathymidylate (Scheme 8). 相似文献
997.
Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) was found to be an effective catalyst for the cross-coupling reaction of sec-butylmagnesium chloride with bromobenzene, β-bromostyrene, and 2-bromopropene to give the corresponding sec-butyl derivatives in exceedingly high yields. 相似文献
998.
Various types of trivalent phosphorus compounds 1 undergo single-electron transfer (SET) to the photoexcited state of rhodamine 6G (Rho+*) in aqueous acetonitrile to quench the fluorescence from Rho+*. The rate constants kp for the overall SET process were determined by the Stern-Volmer method. The rate is nearly constant at a diffusion-controlled limit in the region of E1/2(1) < 1.3 V (vs Ag/Ag+), whereas log kp depends linearly on E1/2(1) in the region of E1/2(1) > 1.3 V, the slope of the correlation line being -alphaF/RT with alpha = 0.2. The potential at which the change in dependence of log kp on E1/2(1) occurs (1.3 V) is in accordance with the value of E1/2(Rho+*) (1.22 V) that has been obtained experimentally. Thus, the SET step is exothermic when E1/2(1) < 1.3 V and endothermic when E1/2(1) > 1.3 V. The alpha-value (0.2) obtained in the endothermic region shows that the SET step from 1 to Rho+* is irreversible in this region. Trivalent phosphorus radical cation 1*+ generated in the SET step undergoes an ionic reaction with water in the solvent rapidly enough to make the SET step irreversible. In contrast, the SET from amines 2 and alkoxybenzenes 3 to Rho+* is reversible when the SET step is endothermic, meaning that the radical cations 2*+ and 3*+ generated in the SET step undergo rapid "back SET" in the ground state to regenerate 2 and 3. 相似文献
999.
Yoshihito Osada Mitsuo Takase 《Journal of polymer science. Part A, Polymer chemistry》1985,23(9):2425-2439
Glow-discharge plasma polymerization of hexamethylcyclotrisiloxane was carried out on the cellulose acetate substrate in the presence of iodine crystal and the effect of I2 doping on liquid permeability such as water, cyclohexane, alcohol homologues, and a water–alcohol mixture was investigated. It was found that I2-doped poly(siloxane) (PHMS–I2) membrane exhibited larger water permeability than nondoped (PHMS) membrane with anomalous pressure dependence (fourth power with pressure gradient). The permeability of alcohol homologues of PHMS membrane increased with increasing the molecular size and the hydrophobicity, whereas that of PHMS–I2 membrane decreased significantly. The presence of a small amount of hemoglobin also increased the water permeability of both membranes. From the results of flow tests of various kinds of fluid it was assumed that these membranes permeate the liquid predominantly by solution-diffusion mechanism. 相似文献
1000.
Etsu Takeuchi Tamotsu Hashimoto Mitsuo Sawamoto Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》1989,27(10):3303-3314
Ethyl 2-(vinyloxy)ethoxyacetate ( 4 ; CH2?CH? OCH2CH2OCH2? COOC2H5), a vinyl ether having both carboxylic acid ester and oxyethylene unit in its pendant, afforded well-defined living polymers when polymerized by the hydrogen iodide/iodine (HI/I2) initiating system in toluene at ?40°C. The polymers possessed a narrow molecular weight distribution (M w/M n ≤ 1.15), and their molecular weight (M n) increased proportionally to monomer conversion or the molar ratio of the monomer to hydrogen iodide. The polymer molecular weight also increased upon addition of a fresh feed of the monomer to a completely polymerized reaction mixture. Polymers of high molecular weights (M n > 5 × 105) and broad molecular weight distributions were obtained by BF3OEt2 in toluene at ?40°C. Polymerization rate of 4 with HI/I2 is ca. 100 times greater than that of the corresponding alkyl vinyl ether, and thus 4 was found to be one of the most reactive vinyl ethers thus far studied. Alkaline hydrolysis of the pendant ester groups of the polymers gave a vinyl ether-based polymeric carboxylic acid 6 with a narrow molecular weight distribution. 相似文献