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61.
Molla Rafiquel Islam Elianne Dahan Sundar Saimani Pudupadi R. Sundararajan 《European Polymer Journal》2012,48(9):1538-1554
Self-assembly of amphiphilic molecules ranging from simple surfactants to block copolymers in a solvent depends on one part of the molecule (one block in block copolymers) being soluble, and the other not. The aggregation of the insoluble segment in the block-selective solvent leads to the self assembly. In this paper, we describe a system of amphiphilic rod–coil and coil–rod–coil molecules, which do not show self assembly in block-selective non-aqueous solvents. We prepared rod–coil molecules based on hydrophilic propylene oxide/ethylene oxide copolymer (PO–EO copolymer) (Jeffamine®) as the flexible segment and photo-conducting large aromatic perylenediimide (PTCDI) as the rod. PO–EO copolymer was attached either to one side of PTCDI (MJ–PTCDI) or both sides (DJ–PTCDI). The former can be considered an inverse macromolecular surfactant, since the tail is hydrophilic and the head is hydrophobic. The DJ–PTCDI is a pseudo Gemini surfactant. Because of the presence of the chromophore, UV–Vis and fluorescent spectra could be used to study the self assembly of these amphiphilic rod coil polymers in solution. PTCDI forms π-interaction mediated aggregates in aqueous solution and these are H-stacked in MJ–PTCDI and J-stacked in DJ–PTCDI. Variable temperature UV and NMR spectra show that the assembly is stable over a large temperature range in water. The aggregates are also stable up to a pH of 12. However, when a non-aqueous solvent is used, no aggregation occurs. This is attributed to the “solvation” of the π-system of the PTCDI. With the addition of water, such solvation seems to be interrupted and aggregation occurs when water becomes a major component. We find that the mole percentage of the aggregates in acetone/water mixtures increases almost linearly with the concentration of water, providing a route to control the extent of aggregation of the chromophores. Due to the long, waxy PO–EO copolymer, MJ–PTCDI and DJ–PTCDI do not show liquid crystalline behavior or nanorod morphology, which were seen with short side chains. The optical microscopy of the bulk material shows aggregated crystals of PTCDI in the waxy matrix, showing that even in the presence of PO–EO copolymer, the molecular assembly of PTCDI takes place in the bulk. Secondary assembly was seen, in that upon ageing of the aqueous solutions, the drop cast films show that the spherical aggregates one-dimensionally coalesced into long fibers. Although UV–Vis spectra indicated no aggregation in non-aqueous solvents, drop-cast films of these solutions show needle-like aggregates and Lego-like assemblies. 相似文献
62.
An unexpected product, 2-oxo-1,2-diphenylethyl benzoate (benzoyl benzoin), was isolated during the attempted Knoevenagel reaction of benzil and dimethylmalonate (or malononitrile) in the presence of potassium carbonate. The product was confirmed by spectral analysis as well as by single crystal studies and a mechanism is proposed to explain its formation. 相似文献
63.
Shyamaprosad Goswami Reshmi Mukherjee Kumaresh Ghosh Ibrahim Abdul Razak S. Shanmuga Sundara Raj Hoong‐Kun Fun 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(4):477-478
In the title cocrystal, 2‐aminopyrimidine–(+)‐camphoric acid (1/1), C4H5N3·C10H16O4, the 2‐aminopyrimidine forms two eight‐membered hydrogen‐bonded rings with two different camphoric acid molecules. This results in infinite wave‐like chains of molecules in which neighbouring chains are connected by weak C—H?O contacts. The five‐membered ring in the acid molecule adopts a half‐chair conformation. 相似文献
64.
Hoong‐Kun Fun R. Sankaranarayanan D. Velmurugan S. Shanmuga Sundara Raj G. Babu P. T. Perumal 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(4):475-476
In the title compound, C26H22N2O2S, the tetrahydropyridine ring has a conformation intermediate between half‐chair and sofa. The tetrahydroquinoline mean plane makes a dihedral angle of 73.3 (1)° with the cyclopentene ring, which adopts an envelope conformation, and an angle of 45.45 (4)° with the indole best plane. The dihedral angle between the benzene and pyrrole rings is 2.6 (1)°. The orientations of the phenyl ring on the sulfonyl group and of the indole are governed by weak C—H?O interactions. The packing of the molecule in the solid state is stabilized by C—H?O and C—H?N hydrogen bonds. 相似文献
65.
Ibrahim Abdul Razak S. Shanmuga Sundara Raj Hoong‐Kun Fun Zhen‐Feng Chen Jing Zhang Ren‐Geng Xiong Xiao‐Zeng You 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(8):e341-e342
In the title compound, C18H16N2O4, the piperidine ring adopts a chair conformation, lying on an inversion centre. The 4‐hydroxybenzyl groups are in quasi‐axial positions. A two‐dimensional network is formed through N—H?O and O—H?O intermolecular hydrogen bonds and C—H?O interactions. 相似文献
66.
Kandasamy Chinnakali S. Shanmuga Sundara Raj Hoong‐Kun Fun Kamaraj Sriraghavan Vayalakkavoor T. Ramakrishnan 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):227-228
In the title compound, C17H21NO3S, the S atom is in a distorted tetrahedral geometry and the N atom exhibits sp2 character. The antiperiplanar conformation is observed for the N and hydroxyl‐O atoms and the torsion angle around the N—C linkage is ?136.3 (2)°. The molecules are linked by O—H?O intermolecular hydrogen bonds to form an infinite one‐dimensional chains along the c axis. 相似文献
67.
A. Subbiah Pandi D. Velmurugan S. Shanmuga Sundara Raj Hoong‐Kun Fun V. Raghukumar V. T. Ramakrishnan 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(6):723-725
In the title compounds, C17H15N3 and C20H22N4, the methyl derivative crystallizes with two molecules in the asymmetric unit, while the N,N‐diethylamino derivative crystallizes with one molecule per asymmetric unit. The biphenyl twist angle for both molecular structures is approximately 45°. The molecular packing is stabilized by N—H?N hydrogen bonds. 相似文献
68.
A. Subbiah Pandi D. Velmurugan S. Shanmuga Sundara Raj Hoong‐Kun Fun P. R. Seshadri D. Thirumalai 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(7):821-824
10‐(4‐Fluorophenyl)‐3,3,6,6,9‐pentamethyl‐3,4,6,7,9,10‐hexahydroacridine‐1,8(2H,5H)‐dione, C24H28FNO2, (I), crystallizes with two crystallographically independent molecules (which differ slightly in conformation), while 10‐(4‐fluorophenyl)‐9‐propyl‐3,3,6,6‐tetramethyl‐3,4,6,7,9,10‐hexahydroacridine‐1,8(2H,5H)‐dione, C26H32FNO2, (II), crystallizes with one molecule per asymmetric unit. In both structures, the central ring in the acridine moiety is in a sofa conformation, while the outer rings adopt intermediate half‐chair/sofa conformations. The central pyridine ring is orthogonal to the substituted phenyl ring. In both structures, the packing of the crystal is stabilized by C—H?O intermolecular hydrogen bonds. 相似文献
69.
Shusheng Zhang Zhongwei Wang Ming Li Kui Jiao Ibrahim Abdul Razak S. Shanmuga Sundara Raj Hoong‐Kun Fun 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):566-568
In both the title structures, O‐ethyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐glucopyranosyl)thiocarbamate, C17H25NO10S, and O‐methyl N‐(2,3,4,6‐tetra‐O‐acetyl‐β‐d ‐glucopyranosyl)thiocarbamate, C16H23NO10S, the hexopyranosyl ring adopts the 4C1 conformation. All the ring substituents are in equatorial positions. The acetoxymethyl group is in a gauche–gauche conformation. The S atom is in a synperiplanar conformation, while the C—N—C—O linkage is antiperiplanar. N—H?O intermolecular hydrogen bonds link the molecules into infinite chains and these are connected by C—H?O interactions. 相似文献
70.
We describe a change of time technique for stochastic control problems with unbounded control set. We demonstrate the technique on a class of maximization problems that do not have optimal controls. Given such a problem, we introduce an extended problem which has the same value function as the original problem and for which there exist optimal controls that are expressible in simple terms. This device yields a natural sequence of suboptimal controls for the original problem. By this we mean a sequence of controls for which the payoff functions approach the value function. 相似文献