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121.
Ifuku S Kamitakahara H Takano T Tanaka F Nakatsubo F 《Organic & biomolecular chemistry》2004,2(3):402-407
Cellulose was reacted with a series of 4-alkoxytrityl chlorides (C(n)TCl, n: number of carbon atoms in a saturated alkyl chain) under homogeneous reaction conditions in LiCl-N,N-dimethyl acetoamide to give a series of 6-O-(4-alkoxytrityl)celluloses (C(n)TC) with a high degree of substitution (DS), from 0.94 to 0.99, and with high regioselectivity at the 6-O position. Solubility of the C(n)TC in nonpolar solvents depended on the alkyl chain length: as the alkyl chain lengthens, cellulose derivatives become more hydrophobic and are readily soluble in nonpolar solvents, but not in polar solvents. Acetates of the C(4)-C(18)TC (C(4)-C(18)TCAc) showed anisotropic structures over melting temperatures (T(m)) examined under a polarized optical microscope (POM). Over isotropization temperatures (T(i)), flow birefringence were detected for C(12)-C(18)TCAc. The T(m) and T(i) decreased linearly with an increasing number of carbon atoms in the alkyl substituent. Wide-angle X-ray scattering (WAXS) studies of C(n)TC indicated that the fully extended side chains were perpendicular to the polymer backbone and interdigitated. These C(n)TC with the improved solubility may be used as starting materials for further derivatization focused on the secondary hydroxyl groups at the C-2 and C-3 positions. 相似文献
122.
Matsumoto A Tanaka T Tsubouchi T Tashiro K Saragai S Nakamoto S 《Journal of the American Chemical Society》2002,124(30):8891-8902
We now report the molecular and crystal structure design of muconic ester derivatives on the basis of crystal engineering using halogen-halogen contacts and CH/pi interactions. The solid-state photoreaction pathway of the dibenzyl (Z,Z)-muconates as the 1,3-diene dicarboxylic acid monomers depends on the structure of the ester groups. The substitution of a halogen atom for the aromatic hydrogen of a benzyl group induces topochemical polymerization to produce stereoregular polymers in a crystalline form, whereas the unsubstituted benzyl derivative isomerizes to yield the corresponding E,E isomer under similar conditions. The topochemical polymerization process is directly confirmed by the fact that the single-crystal structures before and after the polymerization are very similar to each other. From the crystal structure analysis for a series of substituted benzyl (Z,Z)- and (E,E)-muconates, it has been revealed that the planar diene moieties are closely packed to form a columnar structure in the crystals. The stacking of the polymerizable monomers is characterized by a stacking distance of 4.9-5.2 A along the columns. This structure is supported by a halogen-halogen interaction between the chlorine or bromine atoms introduced at the p position of the benzyl groups in addition to an aromatic stacking due to the CH/pi interaction between the benzylic methylene hydrogens and aromatic rings. The design of a monomer packing corresponds to the type and position of the introduced halogen atom and also the polymorphs. To make a stacking distance of 5 A using both halogen-halogen and CH/pi interactions as supramolecular synthons is important for the molecular design of muconic ester derivatives appropriate for topochemical polymerization. 相似文献
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125.
M. Iftekhar Shams Shinsuke Ifuku Masaya Nogi Takeshi Oku Hiroyuki Yano 《Applied Physics A: Materials Science & Processing》2011,102(2):325-331
This paper demonstrates the preparation of chitin nanofibers from crab shells using a simple mechanical treatment. The nanofibers
are small enough to retain the transparency of neat acrylic resin. Possessing hydroxyl and amine/N-acetyl functionalities, water suspension of chitin nanofibers was vacuum-filtered 9 times faster than cellulose nanofibers
to prepare a nanofiber sheet of 90 mm in diameter. This is a prominent advantage of chitin nanofibers over cellulose nanofibers
in terms of commercial application. Interestingly, chitin acrylic resin films exhibited much higher transparency than cellulose
acrylic resin films owing to the close affinity between less hydrophilic chitin and hydrophobic resin. Furthermore, the incorporation
of chitin nanofibers contributes to the significant improvement of the thermal expansion and mechanical properties of the
neat acrylic resin. The properties of high light transmittance and low thermal expansion make chitin nanocomposites promising
candidates for the substrate in a continuous roll-to-roll process in the manufacturing of various optoelectronic devices such
as flat panel displays, bendable displays, and solar cells. 相似文献
126.
Cover Picture: Controlled Synthesis of Nanoporous Nickel Oxide with Two‐Dimensional Shapes through Thermal Decomposition of Metal–Cyanide Hybrid Coordination Polymers (Chem. Eur. J. 9/2015) 下载免费PDF全文
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128.
Takeshi Sakai Takehiko Yagi Ryosuke Takeda Toshiki Hamatani Yuki Nakamoto Hirokazu Kadobayashi 《高压研究》2020,40(1):12-21
ABSTRACTBoth micro-paired and conical support type double-stage diamond anvil cells (ds-DAC) were tested using a newly synthesized ultra-fine nano-polycrystalline diamond (NPD). Well-focused X-ray sub-micron beam and the conically supported 2nd stage anvils (micro-anvils) with 10?μm culet enable us to obtain good quality X-ray diffraction peaks from the sample at around 400?GPa. The relationship between confining pressure and sample pressure depends heavily on the initial height (thickness) of micro-anvils, the difference of a few micrometers leads to a quite different compression path. The conical support type is a solution to retain both enough thickness and strength of micro-anvils at higher confining pressure conditions. All conical support ds-DAC experiments terminated by the failure of the 1st stage anvil instead of 2nd one. The combination of ultra-fine NPD 2nd stage anvil and NPD 1st stage anvil opens a new frontier for measurement of the X-ray absorption spectrum above 300?GPa. 相似文献
129.
Tatsuya Higashi Koichi Ito Misato Narushima Takahiro Sugiura Shinsuke Inagaki Jun Zhe Min Toshimasa Toyo'oka 《Biomedical chromatography : BMC》2011,25(11):1175-1180
A method for the quantification of progesterone (PROG) in human saliva using liquid chromatography–electrospray ionization–tandem mass spectrometry (LC‐ESI‐MS/MS) has been developed and validated. The saliva was deproteinized with acetonitrile, purified using a Strata™‐X cartridge, and subjected to LC‐ESI‐MS/MS. Quantification was based on selected reaction monitoring, and deuterated PROG was used as the internal standard. This method allowed the reproducible (intra‐ and inter‐assay relative standard deviations, <2.2%) and accurate (analytical recovery, 96.6–99.7%) quantification of the salivary PROG using a 400 μL sample, and the limit of quantification was 12.5 pg/mL. The developed method enabled detection of the variation in the salivary PROG concentrations of healthy volunteers during the menstrual cycle and measurement of the salivary concentrations of pregnant women. The method is expected to be an alternative to the blood PROG monitoring in clinical examinations, because saliva collection is easy, non‐invasive and repeatable. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
130.