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41.
Chiral polythiophenes (PTs), in sharp contrast to other optically active polymers, exhibit optical activity in the pi-pi* transition region which is derived from the chirality of the main chain when they self-assemble to form a supramolecular pi-stacked aggregate with intermolecular interactions in a poor solvent or in a film. We now report that the regioregular, optically active PT poly[(R)-3-[4-(4-ethyl-2-oxazolin-2-yl)phenyl]thiophene] (poly-1) exhibits unique split-type induced circular dichroism (ICD) in the pi-pi* transition region of the main chain upon complexation with various metal salts such as trifluoromethanesulfonates of copper(I), copper(II), silver(I), and zinc(II), and iron(II) perchlorate in chloroform, which is a good solvent for poly-1. The appearance of ICD and slight changes in the UV/Vis spectra (no color change), except for the zinc salts, indicated that the chirality may not be induced by chiral pi-stacked aggregates of poly-1, but by the chirality of the main chain, for example, a predominantly one-handed helical structure induced by intermolecular coordination of the oxazoline groups to metal ions. The sign of the Cotton effect depends on the metal salt; most metal salts induced ICDs with similar Cotton-effect patterns, while zinc salts caused an inversion of the signs of the Cotton effect of poly-1 accompanied by a gradual red shift in the absorption of up to 125 nm. The changes in the conformation and the size of the poly-1 aggregates induced by different metal salts were also investigated by (1)H NMR titrations, static light scattering (SLS), atomic force microscopy (AFM), and membrane filtration. On the basis of these results, we propose a possible model for the chiral supramolecular aggregates of poly-1 with metal salts. 相似文献
42.
Otsuka H Kijima H Hirata E Shinzato T Takushi A Bando M Takeda Y 《Chemical & pharmaceutical bulletin》2003,51(3):286-290
Five megastigmane glucosides were isolated from the leaves of Glochidion zeylanicum. One of them was a known compound, blumenol C O-beta-D-glucopyranoside (1), and the structures of the four new compounds, glochidionionosides A-D (2-5), were mainly elucidated by spectroscopic methods, including a modified Mosher's method. The absolute configurations of the six-membered ring of glochidionionoside D (5) were deduced by beta-D-glucopyranosylation-induced shift trends in the (13)C-NMR spectra and confirmed by X-ray analysis as its p-bromobenzoate (5b), and the axis chirality of C-7 was determined to be R. 相似文献
43.
Optically active polyisocyanides (poly(iminomethylenes)) have been prepared with much interest in developing new functional materials. Polyisocyanides have been considered to have a stable 4(1) helical conformation even in solution when they have a bulky side group. However, the conformational characteristics of poly(phenyl isocyanide) (PPI) derivatives are still under debate. We now report that an optically inactive PPI derivative, poly(4-carboxyphenyl isocyanide) (poly-1), shows optical activity in the polymer backbone induced by external, chiral stimuli through acid-base interactions under thermodynamic control and exhibits induced circular dichroism (ICD) in the UV-visible region in DMSO. The ICD intensities of the poly-1-chiral amine complexes in DMSO gradually increased with time, and, in one case, the value reached 3 times that of the original value after 2 months at 30 degrees C. The conformational changes also occurred very slowly for poly-1 alone and its ethyl ester with time on the basis of (1)H NMR spectroscopic analysis. These results indicate that PPIs bearing a less bulky substituent may not have a 4(1) helical conformation but have a different type of prochiral conformation, for instance, an s-trans (zigzag) structure which may transform to a dynamic, one-handed helical conformation when the PPIs have a functional group capable of interacting with chiral compounds. The mechanism of helicity induction on poly-1 through a dynamic conformational transition is discussed on the basis of the above results together with molecular dynamic simulation results for PPI. 相似文献
44.
Ooi T Takahashi M Yamada M Tayama E Omoto K Maruoka K 《Journal of the American Chemical Society》2004,126(4):1150-1160
A series of (2,7-disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) (2) has been readily prepared in situ by treatment of the requisite 2,7-disubstituted-1,8-biphenylenediol (1) with Me3Al (2 equiv) in CH2Cl2 at room temperature; this primarily relies on the successful establishment of a new synthetic procedure of 1 starting from inexpensive m-anisidine. Evaluation of 2 as a bidentate organoaluminum Lewis acid has been performed by the reduction of ketonic substrates using Bu3SnH as a hydride source in comparison to the conventional monodentate Lewis acid dimethylaluminum 2,6-xylenoxide (11), uncovering the significantly high activation ability of 2 toward carbonyl. Particularly, (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) (2a) exerted the highest reactivity, which has also been emphasized in the Mukaiyama aldol reaction. The structure of the bidentate Lewis acid 2 was unambiguously determined by single-crystal X-ray diffraction analysis of 2g possessing a bulky 3,5-di-tert-butylphenyl substituent, revealing the rigid dimeric assembly in the solid state. The double electrophilic activation of carbonyl substrate by 2a has been supported by low-temperature 13C NMR analysis as well as theoretical study using the Gaussian 98 program. Moreover, unique stereoselectivity has been observed in the 2a-promoted Mukaiyama Michael addition, and highly chemoselective functionalization of carbonyl compounds in the presence of their acetal counterparts has been realized using 2a. Finally, the effectiveness of 2a for the activation of ether functionality has been demonstrated in the Claisen rearrangement of allyl vinyl ethers. 相似文献
45.
Copper(II)-acid co-catalyzed intermolecular substitution of electron-rich aromatics with diazoesters
The intermolecular aromatic substitution of N,N-dialkylanilines and alkoxybenzenes with diazoesters is shown to proceed in the presence of catalytic amounts of both copper(II) salt and acid (Lewis or Brønsted). This method is a mild and rare metal-free C-C bond formation reaction between aromatic (sp2) and aliphatic (sp3) carbons. 相似文献
46.
Takahashi K Hasegawa Y Sakamoto R Nishikawa M Kume S Nishibori E Nishihara H 《Inorganic chemistry》2012,51(9):5188-5198
We previously reported that an Fe(II) complex ligated by two (Z)-2,6-di(1H-pyrazol-1-yl)-4-styrylpyridine ligands (Z-H) presented a solid state ligand-driven light-induced spin change (LD-LISC) upon one-way Z-to-E photoisomerization, although modulation of the magnetism was trivial at ambient temperatures (Chem. Commun.2011, 47, 6846). Here, we report the synthesis of new derivatives of Z-H, Z-CN and Z-NO(2), in which electron-withdrawing cyano and nitro substituents are introduced at the 4-position of the styryl group to attain a more profound photomagnetism at ambient temperatures. Z-CN and Z-NO(2) undergo quantitative one-way Z-to-E photochromism upon excitation of the charge transfer band both in acetonitrile and in the solid state, similar to the behavior observed for Z-H. In solution, these substituents stabilized the low-spin (LS) states of Z-CN and Z-NO(2), and the behavior was quantitatively analyzed according to the Evans equation. The photomagnetic properties in the solid state, on the other hand, cannot be explained in terms of the substituent effect alone. Z-CN displayed photomagnetic properties almost identical to those of Z-H. Z-CN preferred the high-spin (HS) state at all temperatures tested, whereas photoirradiated Z-CN yielded a lower χ(M)T at ambient temperatures. The behavior of Z-NO(2) was counterintuitive, and the material displayed surprising photomagnetic properties in the solid state. Z-NO(2) occupied the LS state at low temperatures and underwent thermal spin crossover (SCO) with a T(1/2) of about 270 K. The photoirradiated Z-NO(2) displayed a higher value of χ(M)T and the modulation of χ(M)T exceeded that of Z-H or Z-CN. Z-NO(2)·acetone, in which acetone molecules were incorporated into the crystal lattice, further stabilized the LS state (T(1/2) > 300 K), thereby promoting large modulations of the χ(M)T values (87% at 273 K and 64% at 300 K) upon Z-to-E photoisomerization. Single crystal X-ray structure analysis revealed that structural factors played a vital role in the photomagnetic properties in the solid state. Z-H and Z-CN favored intermolecular π-π stacking among the ligand molecules. The coordination sphere around the Fe(II) nucleus was distorted, which stabilized the HS state. In contrast, Z-NO(2)·acetone was liberated from such intermolecular π-π stacking and coordination distortion, resulting in the stabilization of the LS state. 相似文献
47.
48.
Hirohito Ikeda Yukiko Sano Tomonori Matsubara Mitsunobu Kawahara Miho Yukawa Masao Fujisawa Eiji Yukawa Hatsumi Aki 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1135-1138
Propericiazine (PCZ) is an antipsychotic agent used for the treatment and the prevention of relapse of schizophrenia. We found that when an oral solution containing PCZ was mixed with a green tea drink, the residual content of PCZ was reduced by forming an insoluble complex between PCZ and tea polyphenol. In this study, the mechanism underlying the incompatibility of PCZ with green tea polyphenol (GTP) in the solution was clarified by isothermal titration microcalorimetry (ITC). Both solutions of 27.4 mM PCZ and 2.2 mM (?)-epigallocatechin gallate (EGCg), which is a main ingredient of GTP, were mixed and then PCZ in the filtrate was reduced to approximately 60 %. According to measurement at 298 K by ITC, PCZ formed an insoluble complex with EGCg at an associate constant (K) of 4.75 × 102 M?1 exothermically, ΔH = ?40.0 kJ mol?1. When (?)-epicatechin gallate (ECg) was used as the GTP, PCZ interacted with ECg with K and ΔH values of 3.74 × 102 M?1 and ?22.1 kJ mol?1, respectively. On the other hand, little heat of the reaction between PCZ and (?)-epigallocatechin or (?)-epicatechin was observed. The results indicated that the main reason for this incompatibility was the formation of an insoluble complex by PCZ and a gallate-type GTP such as EGCg and ECg in the aqueous solution. 相似文献
49.
Makoto Kunisada Taro Masaki Ryusuke Ono Hironobu Morinaga Eiji Nakano Flandiana Yogianti Kunihiro Okunishi Hiroshi Sugiyama Chikako Nishigori 《Photochemistry and photobiology》2013,89(3):649-654
The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage. 相似文献
50.
Di(triptycyl)carbene: a fairly persistent triplet dialkylcarbene 总被引:1,自引:0,他引:1
Iiba E Hirai K Tomioka H Yoshioka Y 《Journal of the American Chemical Society》2002,124(48):14308-14309
The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes. 相似文献