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71.
Shitomi Katayama Hideichi Horikawa Noboru Masuda 《Journal of polymer science. Part A, Polymer chemistry》1971,9(5):1173-1188
Anionic copolymerizations of acrylonitrile (monomer 1) with β-propiolactone (monomer 2) and the structures of the resulting copolymers were studied. The copolymerization with sodium cyanide in N,N-dimethylformamide gave copolymers of the structure I containing acid anhydride linkage in the molecular chains, with the monomer reactivity ratios, r1 = 1.20, r2 = 0.00. The copolymerization with potassium hydroxide gave either copolymers of the structure II (r1 = 0.00, r2 = 3.64 at 30°C; r1 = 0.00, r2 = 5.00 at 40°C) in N,N-dimethylformamide or only β-propiolactone homopolymer in toluene. 相似文献
72.
Yo Ueda K
ichi Mori Keiki Kouno Tokihiro Nhya 《Journal of mass spectrometry : JMS》1976,11(10):1027-1036
The mass spectra of 30 sulfinamide derivatives (RSONHR', R' alkyl or p-XC6H4) are reported. Most of the spectra had peaks attributable to thermal decomposition products. For some compounds these were identified by pyrolysis under similar conditions to be: RSO2NHR', RSO2SR, RSSR and NH2R' (in all kinds of sulfinyl amides); RSNHR' (in the case of arylsulfinyl arylamides); RSO2C6H4NH2, RSOC6H4NH2 and RSC6H4NH2 (in the case of arylsulfinyl arylamides of the type of X = H) The mass spectra of the three thermally stable compounds showed that there are several kinds of common fragment ions. The mass spectra of the thermally labile compounds had two groups of ions; (i) characteristic fragment ions of the intact molecules and (ii) the molecular ions of the thermal decomposition products. It was concluded that the sulfinamides give the following ions after electron impact: [M]+, [M ? R]+, [M ? R + H]+, [M ? SO]+, [RS]+, [NHR']+, [NHR' + H]+, [RSO]+, [RSO + H]+, [R]+, [R + H]+, [R']+ and [M ? OH]+, and that the thermal decomposition products give the following ions: [RSO2SR]+, [RSSR]+, [M ? O]+, [M + O]+ and [RSOC6H4NH2]+. 相似文献
73.
Dr. Kazukuni Tahara Yuki Yamamoto Dr. Dustin E. Gross Hiroyoshi Kozuma Yoko Arikuma Dr. Koji Ohta Dr. Yoshiko Koizumi Yuan Gao Dr. Yo Shimizu Prof. Shu Seki Dr. Kenji Kamada Prof. Jeffrey S. Moore Prof. Yoshito Tobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11251-11260
We present herein the synthesis and properties of the largest hitherto unknown graphyne fragment, namely trigonally expanded tetrakis(dehydrobenzo[12]annulene)s (tetrakis‐DBAs). Intramolecular three‐fold alkyne metathesis reactions of hexakis(arylethynyl)DBAs 9 a and 9 b using Fürstner’s Mo catalyst furnished tetrakis‐DBAs 8 a and 8 b substituted with tert‐butyl or branched alkyl ester groups in moderate and fair yields, respectively, demonstrating that the metathesis reaction of this protocol is a powerful tool for the construction of graphyne fragment backbones. For comparison, hexakis(arylethynyl)DBAs 9 c – g have also been prepared. The one‐photon absorption spectrum of tetrakis‐DBA 8 a bearing tert‐butyl groups revealed a remarkable bathochromic shift of the absorption cut‐off (λcutoff) compared with those of previously reported graphyne fragments due to extended π‐conjugation. Moreover, in the two‐photon absorption spectrum, 8 a showed a large cross‐section for a pure hydrocarbon because of the planar para‐phenylene‐ethynylene conjugation pathways. Hexakis(arylethynyl)‐DBAs 9 c – e and 9 g and tetrakis‐DBA 8 b bearing electron‐withdrawing groups aggregated in chloroform solutions. Comparison between the free energies of 9 e and 8 b bearing the same substituents revealed the more favorable association of the latter due to stronger π–π interactions between the extended π‐cores. Polarized optical microscopy observations, DSC, and XRD measurements showed that 8 b and 9 e with branched alkyl ester groups displayed columnar rectangular mesophases. By the time‐resolved microwave conductivity method, the columnar rectangular phase of 8 b was shown to exhibit a moderate charge‐carrier mobility of 0.12 cm2 V?1 s?1. These results indicate that large graphyne fragments can serve as good organic semiconductors. 相似文献
74.
Lou Y Horikawa M Kloster RA Hawryluk NA Corey EJ 《Journal of the American Chemical Society》2004,126(29):8916-8918
A novel chiral Rh(II) catalyst (1) is introduced for the [2 + 1]-cycloaddition of ethyl diazoacetate to terminal acetylenes and olefins with high enantioselectivity. The catalyst 1 consists of one acetate bridging group and three mono-N-triflyldiphenylimidazoline-2-one bidentate ligands (DPTI) spanning the Rh(II)-Rh(II) metallic center in a structure that was determined by single-crystal X-ray diffraction analysis. A rational mechanism is advanced that provides a straightforward explanation for the enantioselectivity and absolute stereochemical course of the [2 + 1]-cycloaddition reactions. A key element in this explanation is the cleavage of one of the Rh-O bonds of the bridging acetate group in the intermediate Rh-carbene complex to form a new pentacoordinate Rh carbene complex (formally 1.5 valent Rh) that can undergo [2 + 2]-cycloaddition with the C-C pi-bond of the acetylenic or olefinic substrate. Reductive elimination of the resulting adduct affords the cyclopropene or cyclopropane product. The C2-symmetry of the two DPTI ligands orthogonal to the bridging acetate also contributes to the high observed enantioselectivity and mechanistic clarity. The catalyst 1, which functions effectively at 0.5 mol %, can be recovered efficiently for reuse. Its ready availability, robustness, and effectiveness suggest it as a useful addition to the list of practical chiral Rh(II) catalysts for synthesis. 相似文献
75.
A Programmable Signaling Molecular Recognition Nanocavity Prepared by Molecular Imprinting and Post‐Imprinting Modifications 下载免费PDF全文
Ryo Horikawa Dr. Hirobumi Sunayama Dr. Yukiya Kitayama Dr. Eri Takano Prof. Dr. Toshifumi Takeuchi 《Angewandte Chemie (International ed. in English)》2016,55(42):13023-13027
Inspired by biosystems, a process is proposed for preparing next‐generation artificial polymer receptors with molecular recognition abilities capable of programmable site‐directed modification following construction of nanocavities to provide multi‐functionality. The proposed strategy involves strictly regulated multi‐step chemical modifications: 1) fabrication of scaffolds by molecular imprinting for use as molecular recognition fields possessing reactive sites for further modifications at pre‐determined positions, and 2) conjugation of appropriate functional groups with the reactive sites by post‐imprinting modifications to develop programmed functionalizations designed prior to polymerization, allowing independent introduction of multiple functional groups. The proposed strategy holds promise as a reliable, affordable, and versatile approach, facilitating the emergence of polymer‐based artificial antibodies bearing desirable functions that are beyond those of natural antibodies. 相似文献
76.
This paper deals with the asymptotic distribution of Wishart matrix and its application to the estimation of the population matrix parameter when the population eigenvalues are block-wise infinitely dispersed. We show that the appropriately normalized eigenvectors and eigenvalues asymptotically generate two Wishart matrices and one normally distributed random matrix, which are mutually independent. For a family of orthogonally equivariant estimators, we calculate the asymptotic risks with respect to the entropy or the quadratic loss function and derive the asymptotically best estimator among the family. We numerically show (1) the convergence in both the distributions and the risks are quick enough for a practical use, (2) the asymptotically best estimator is robust against the deviation of the population eigenvalues from the block-wise infinite dispersion. 相似文献
77.
The particle scattering function P(k) is approximately evaluated for the Kratky–Porod wormlike chain with a circular cross section to examine the effect of chain diameter d on the scattering curve of k2P(k) versus k, the magnitude of the scattering vector, for stiff chains and also the applicability of the cross‐section plot of ln[kP(k)] versus k2 to them. In the evaluation, series expansions from the rod and coil limits up to the fifth‐order and third‐order deviations, respectively, are combined together. The major results or conclusions derived are as follows. First, the conventional equation, P(k) = P0(k) exp(?k2d2/16), for straight cylinders overestimates k2P(k) at relatively large values of k, whereas its alternative, P(k) = P0(k)[2J1(kd/2)/(kd/2)]2, is a good approximation to exact P(k) unless contour length L is shorter than 10d. Here, P0(k) denotes the scattering function for the chain contour, and J1(x) is the Bessel function of the first order. Second, as d is increased for a fixed value of L (relative to the Kuhn segment length), the k2P(k)–k curve lowers with a pronounced maximum, and the peak position shifts to a lower scattering angle. Third, if the chain is somewhat flexible, the cross‐section plot has an approximately linear region, with a slope fairly close to ?d2/16 expected from the aforementioned conventional equation. This plot for rods appreciably bends down, and thus the experimental observation of an approximately linear relation (over a wide k range) implies that, in contrast to the prevailing notion, the polymer examined is not completely rigid but instead is somewhat flexible. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1398–1407, 2004 相似文献
78.
79.
Yo Nakamura Takashi Norisuye Akio Teramoto 《Journal of Polymer Science.Polymer Physics》1991,29(2):153-159
Second virial coefficients A2 and third virial coefficients A3 for benzene solutions of ten polystyrene fractions ranging in weight-average molecular weight Mw from 104 to 2 × 107 at 25°C were determined by light scattering. The third coefficient is represented approximately by A3 = 8.0 × 10?6 M mol g?3 cm6 for Mw above 105. In this molecular weight region, the factor g defined by A3/AMw/ This trend of g is consistent with predictions of early two-parameter theories but not with those of renormalization group theories. In particular, quantitative agreement is observed between the present experiments (for Mw ? 2 × 105) and the mean-field two-parameter theory of Stockmayer and Casassa. 相似文献
80.
The temperature and spectral dependences of the coefficients R i2* of the quadratic electro-optic effect (EOE) in triglycine sulphate crystals with 5% L-threonine admixture have been calculated using the temperature and spectral dependences of the refractive indices n i . It is established that the coefficients R i2* of the admixture-containing triglycine sulphate crystals exhibit weak spectral and temperature dependences. In the polar direction, R i2* are substantially different from the coefficients of admixture-free triglycine sulphate crystals. This indicates the occurrence of a bias field, the predominant orientation of the dipole moment of the polar defect, and a decrease in the spontaneous polarization in admixture-containing crystals. 相似文献