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1.
D. Amutha Rani Y. Yamamoto S. Mohri M. Sivakumar Y. Tsujita H. Yoshimizu 《Journal of Polymer Science.Polymer Physics》2003,41(3):269-273
In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003 相似文献
2.
S. Mohri D. Amutha Rani Y. Yamamoto Y. Tsujita H. Yoshimizu 《Journal of Polymer Science.Polymer Physics》2004,42(2):238-245
Syndiotactic polystyrene (sPS) has various crystalline forms such as α, β, γ, and δ forms, and a mesophase depending on the preparation method. In this study, we focused on the mesophase with the molecular cavity of sPS, which is obtained by step‐wise extraction of the guest molecules from the sPS δ form. To prepare the mesophase containing different shapes and sizes of the cavity, two kinds of the sPS δ form membrane cast from either toluene or chloroform solution were first prepared and then the guest molecules were removed by a step‐wise extraction method using acetone and methanol. We could succeed in the preparation of two kinds of mesophase with different shapes and sizes of the molecular cavity. Either toluene or chloroform vapor sorption to the sPS mesophase membranes was examined at 25 °C. Sorption analysis indicates that the mesophase with large molecular cavities can mainly sorb large molecules; on the other hand, the mesophase with small cavities can sorb only the small molecules, and is unable to sorb a large amount of large molecule because the cavity was too small to sorb the large molecules. Therefore, the sPS mesophase membrane has sorption selectivity based on the size of the molecular cavity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 238–245, 2004 相似文献
3.
4.
[reaction: see text] We describe the synthesis of alpha,alpha-dibromomethyl ynones (8) and their subsequent derivatization to vinyl acetates (10). These vinyl acetates feature a 1,1-dibromo-olefin moiety, which is readily exploited in palladium-catalyzed Sonogashira, Stille, and Suzuki cross-coupling reactions with alkynes, stannanes, and boronic acids, respectively. A novel one-pot process then directly converts the resulting vinyl acetates 11-13 to the vinyl triflate derivatives 14a-j. 相似文献
5.
Perchloric acid supported on silica gel acts as an excellent reagent system in converting glucals into 2,3-unsaturated-O-glucosides in good to excellent yields in short reaction time with good alpha selectivity. Primary, secondary, and allylic alcohols, phenols, and thiols react with 3,4,6-tri-O-acetyl glucal with equal ease. In addition to this, a chiral furan diol is obtained from unprotected D-glucal or D-galactal in good yields. 相似文献
6.
Two series of monodisperse cross-conjugated oligomers based on enyne repeat units have been realized. The first class of molecules, iso-polytriacetylenes (iso-PTAs, 2), was divergently synthesized using an iterative sequence of palladium-catalyzed cross-coupling reactions of vinyl triflate 5 with terminal alkynes. The second series of oligoenynes (17-20) are based on an octatetrayne backbone, and result from homocoupling of the differentially protected iso-PTA oligomers 8-11. The longest member of this series, 20, spans ca. 5.6 nm from Si atom to Si atom and is composed of a contiguous sequence of 44 sp and sp(2) carbons. The lowest energy electronic absorption band for iso-PTA dimers in the progression 13 --> 9 --> 16 is consistently red-shifted as a result of extending the cross-conjugated structure. A similar comparison within each series (i.e., 16, 6-7, or 17-20), however, suggests little effect on the electronic characteristics of these molecules as oligomer length is increased. The solid-state properties of one derivative, 17, are also described. 相似文献
7.
Subratanath Koner Masaru TsutakeIsoroku Nagasawa Ryuichi IkedaPratap K. Saha Alok K. MukherjeeSurajit Banerjee 《Journal of Molecular Structure》2002,608(1):63-69
The complex bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate undergoes a first-order thermochromic phase transition at ca. 476 K, changing its color from orange to red. The room temperature X-ray crystal structure determination showed that the nickel ion possesses a square-planar geometry with two five membered chelate rings, in the δλ conformation, forming the NiN4 chromophore. The broad-line 1H NMR indicates the onset of a dynamic disorder of diamine chelate rings at the phase transition temperature region, while T1 measurement of 1H affords the activation energy of the puckering metal chelate rings to be 26 kJ mol−1. The electronic spectrum revealed that a weakening of ligand field around the nickel is associated with the phase transition. 相似文献
8.
A silver selective electrode based on TEPQA‐MCM‐41 material was developed and used for the selective determination of Ag+ ion in various samples. The effect of various plasticizers i. e. dimethyl phthalate (DMP), Tris(ethylhexyl)phosphate (TEP), bis‐(2‐ethylhexyl)sebacate (BEHS), bis‐(2‐ethylhexyl)adipate (BEHA) was investigated. The electrode of the composition of 2 : 1 : 77 : 12 : 8 (w/w, %) of TEPQA‐MCM‐41 : NaTPB : Graphite powder : paraffin oil : DMP respectively, works satisfactorily in a wide concentration range of 1.3×10?9 M–1.0×10?1 M for Ag+ ion with a lower detection limit (LOD) of 1.0×10?9 M and has Nernstian slope of 63.4 1 mV/decay. The electrode can be used in a pH range of 2.3 to 6.7 for a period of 3 months without any divergence in potential response. The selectivity coefficient calculated by fixed interference method indicates the high selectivity of the electrode towards Ag+ ion over other tested cations. 相似文献
9.
Moriarty RM Rani N Enache LA Rao MS Batra H Guo L Penmasta RA Staszewski JP Tuladhar SM Prakash O Crich D Hirtopeanu A Gilardi R 《The Journal of organic chemistry》2004,69(6):1890-1902
A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)). 相似文献
10.
MacLean EJ Harris KD Kariuki BM Kitchin SJ Tykwinski RR Swainson IP Dunitz JD 《Journal of the American Chemical Society》2003,125(47):14449-14451
The transformation of ammonium cyanate into urea, first studied over 170 years ago by W?hler and Liebig, has an important place in the history of chemistry. To understand the nature of this solid state reaction, knowledge of the crystal structure of ammonium cyanate is a prerequisite. Employing neutron powder diffraction, we demonstrate conclusively that, in the structure of ammonium cyanate, the NH(4)(+) cation forms N-H...N hydrogen bonds to four cyanate N atoms at alternate corners of a distorted cube, rather than our previously proposed alternative arrangement with N-H...O hydrogen bonds to cyanate O atoms at the other four corners. 相似文献