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91.
Isoguanosine ( 3 ) underwent a coupling reaction with diaryl disulfides in the presence of tri‐n‐butylphosphine when its 6‐amino group was protected by N,N‐dimethylaminomethylidene. The synthesis of 5′‐deoxy‐N3,5′‐cycloisoguanosine ( 6 ) and its 2′,3′‐O‐isopropylidene derivative ( 11 ) were accomplished in excellent yields from isoguanosines ( 3 & 10 ) in the presence of triphenylphospine and carbon tetrachloride in pyridine. Chlorination at the 5′‐position of isoguanosine ( 3 ) with thionyl chloride followed by the aqueous base‐promoted cyclization afforded the same product 6 . The structures were elucidated by spectroscopic analysis including IR, UV, 1‐D and 2‐D NMR. 相似文献
92.
Dr. Wangdong Zeng Dr. Zhe Sun Dr. Tun Seng Herng Dr. Théo P. Gonçalves Dr. Tullimilli Y. Gopalakrishna Prof. Kuo‐Wei Huang Prof. Jun Ding Prof. Jishan Wu 《Angewandte Chemie (International ed. in English)》2016,55(30):8615-8619
The challenging synthesis of a laterally extended heptazethrene molecule, the super‐heptazethrene derivative SHZ‐CF3 , is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ‐CF3 exhibits an open‐shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives. An intermediate dibenzo‐terrylene SHZ‐2H was also obtained during the synthesis. This study provides a new synthetic method to access large‐size quinoidal polycyclic hydrocarbons with unique physical properties. 相似文献
93.
Extended Bis(benzothia)quinodimethanes and Their Dications: From Singlet Diradicaloids to Isoelectronic Structures of Long Acenes 下载免费PDF全文
Dr. Shaoqiang Dong Dr. Tun Seng Herng Dr. Tullimilli Y. Gopalakrishna Dr. Hoa Phan Zheng Long Lim Pan Hu Prof. Richard D. Webster Prof. Jun Ding Prof. Chunyan Chi 《Angewandte Chemie (International ed. in English)》2016,55(32):9316-9320
Extended bis(benzothia)quinodimethanes and their dications were synthesized as stable species. The neutral compounds mainly have a quinoidal structure in the ground state but show increased diradical character with extension of the central quinodimethane unit. The dications exhibit similar electronic absorption spectra, NMR spectra, NICS values, and diatropic ring currents to their aromatic all‐carbon acene analogues and thus can be regarded as genuine isoelectronic structures of pentacene, hexacene, and heptacene, respectively. Our research gave some insights into the design and synthesis of stable longer acene analogues. 相似文献
94.
We describe the synthesis and characterization of two novel azo ligands, 4,5-dihydroxy-3,6-bis(2-hydroxyphenylazo)-2,7 naphthalene
disulfonic acid (H2L) and 4,5-dihydroxy-3,6-bis(2-hydroxy-4-sulfophenylazo)-2,7-naphthalenedisulfonic acid (H2L1). The Cu(II), Ni(II), and Co(II) complexes of these ligands were prepared and characterized by infrared, UV–Vis, 1H- and 13C-NMR spectra, atomic absorption spectroscopy, mass spectrometry, elemental analyses, thermogravimetric analysis, conductivity,
cyclic voltammetry, and magnetic measurements. The results suggest that the complexes have a 2:1 (metal:ligand) molar ratio,
involving binuclear azo ligands with an ONO donor set. Metal ion uptake studies were conducted with a batch technique. Preliminary
histological studies were also made. The results indicate that the azo ligands have high thermal stability, good metal extraction
capacity, and favorable dying properties with certain tissues. 相似文献
95.
Tun Hai Xu Gang Lv Tong Hua Liu Ya Juan Xu Yun Shan Si Sheng Xu Xie Hong Feng Zhao Dong Han Dong Ming Xu 《中国化学快报》2008,19(7):817-820
A new tdterpenoid glycoside, 3-β-O-β-D-glucopyranosyl presenegenin 28-O-α-L-arabipyranosyl(1 → 3)-6-β- xylopyranosyl(1 → 4)-[β-D-apiofuranosyl(1 → 3)]-Ct-L-rhamnopyranosyl(1 → 2)-[α-L-rhamnopyranosyl(1 → 3)]-β-D-fucopyranosyl ester (1) was isolated from the Polygala tenuifolia Willd., together with two known saponins, including polygalasaponinXXIV (2) and polygalasaponinXXVIII (3). The structure of new compound was elucidated by spectroscopic methods. 相似文献
96.
Unsworth LD Tun Z Sheardown H Brash JL 《Journal of colloid and interface science》2005,281(1):112-121
Physical property studies of surfaces formed by chemisorption of polyethylene oxide (PEO) onto gold are reported. Such surfaces have potential as model materials for elucidation of the mechanism of resistance to protein adsorption by PEO surfaces. Thiolated monomethoxy poly(ethylene oxide) (PEO) was chemisorbed onto gold-coated silicon wafers under various conditions such that different surface chain densities were achieved. Chain density was varied by controlling PEO solubility (proximity to cloud-point conditions) as well as chemisorption time. Films prepared with PEO of molecular weight 750, 2000, and 5000 g/mol were studied. Chain densities determined in the dry state by ellipsometry were found to be in the range of 0.4-0.7, 0.33-0.58, and 0.12-0.30 chains/nm(2) for MW 750, 2000, and 5000 PEO, respectively. Chain density was found to decrease with increasing molecular weight and to increase as cloud-point conditions were approached. PEO-layer mass densities and chain densities were determined independently by neutron reflectometry. Under low-solubility conditions and for a 4-h chemisorption time, film mass and chain density values of 1.0 +/-0.3 g cm(-3) and 1.8 +/- 0.9 chains/nm(2) were found for MW 750 PEO, and 0.82 +/- 0.02 g cm(-3) and 0.23 +/- 0.07 chains/nm(2) for MW 5000 PEO. Ellipsometry data for these systems yielded graft densities of 0.63 +/- 0.13 and 0.30 +/- 0.02 chains/nm(2), respectively. Using the mass densities obtained from the neutron data in the ellipsometry calculations, chain densities of 0.6 +/- 0.3 and 0.25 +/- 0.02 chains/nm(2), respectively, were obtained for the MW 750 and 5000 films. The ellipsometry and neutron data for the MW 5000 system are thus in agreement within experimental error. In general, the chain-density values are much higher than those corresponding to layers of unperturbed random coil PEO ("mushrooms"), suggesting that the PEO layers are in the brush regime with the chains in an extended conformation. 相似文献
97.
Global Aromaticity in Macrocyclic Cyclopenta‐Fused Tetraphenanthrenylene Tetraradicaloid and Its Charged Species 下载免费PDF全文
Dr. Xuefeng Lu Dr. Tullimilli Y. Gopalakrishna Dr. Hoa Phan Dr. Tun Seng Herng Dr. Qing Jiang Chunchen Liu Dr. Guangwu Li Prof. Jun Ding Prof. Jishan Wu 《Angewandte Chemie (International ed. in English)》2018,57(40):13052-13056
A stable cyclopenta‐fused tetraphenanthrenylene macrocycle, CPTP‐M , was synthesized, and the structure was confirmed by X‐ray crystallographic analysis. It exhibits a large radical character (number of unpaired electron, NU=3.52) and a small singlet–triplet energy gap (ΔES‐T=?2.8 kcal mol?1 by SQUID). Its backbone contains 60 ([4n]) conjugated π electrons and is globally antiaromatic. NMR measurements and theoretical calculations revealed that its dication/dianion is globally aromatic owing to the existence of [4n?2]/[4n+2] π‐conjugated electrons. Remarkably, the ring‐current map of the tetraanion shows a unique ring‐in‐ring structure, with a diamagnetic outer ring and a paramagnetic inner ring. Accordingly, both the inner‐rim and outer‐rim protons are deshielded in its 1H NMR spectrum. The tetraanion can be regarded as an isoelectronic structure of the known octulene, which shows similar electronic properties. 相似文献
98.
Dr. Anup Rana Yongseok Hong Dr. Tullimilli Y. Gopalakrishna Dr. Hoa Phan Dr. Tun Seng Herng Priya Yadav Prof. Jun Ding Prof. Dongho Kim Prof. Jishan Wu 《Angewandte Chemie (International ed. in English)》2018,57(38):12534-12537
The synthesis of a bithiophene‐bridged 34π conjugated aromatic expanded porphycene 1 and a cyclopentabithiophene bridged 32π conjugated anti‐aromatic expanded porphycene 2 by a McMurry coupling strategy is presented. Magnetic measurements and theoretical calculations reveal that both 1 and 2 exhibit an open‐shell singlet ground state with significant radical character (y0=0.63 for 1 ; y0=0.68, y1=0.18 for 2 ; y0: diradical character, y1: tetraradical character) and a small singlet–triplet energy gap (ΔES‐T=?3.25 kcal mol?1 for 1 and ΔES‐T=?0.92 kcal mol?1 for 2 ). Despite the open‐shell radical character, both compounds display exceptional stability under ambient air and light conditions owing to effective delocalization of unpaired electrons in the extended cyclic π‐conjugation pathway. 相似文献
99.
Mathematical Programming - We study the geometry of convex optimization problems given in a Domain-Driven form and categorize possible statuses of these problems using duality theory. Our duality... 相似文献
100.