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111.
Kozo Arai Atsushi Matsunaga Masaru Yoneyama Shoji Takigami Yoshio Nakamura Haydn E. Edwards Glyn O. Phillips 《Journal of polymer science. Part A, Polymer chemistry》1993,31(1):249-258
The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc. 相似文献
112.
Vinayak Juvekar Chang Su Lim Dong Joon Lee Sang Jun Park Gyeong Ok Song Hyuk Kang Hwan Myung Kim 《Chemical science》2021,12(1):427
Two-photon photodynamic therapy (TP-PDT) is a promising approach for the treatment of cancer because of its better penetration depth and superior spatial selectivity. Here, we describe an azo group containing cyclized-cyanine derivatives (ACC1 and ACC2) as a two-photon activated, type I based photosensitizer (PS). These small-molecule and heavy atom-free organic dyes showed marked reactive oxygen species (ROS)-generating ability under physiological conditions, as well as fast loading ability into the cells and negligible dark toxicity. Live cell analyses with one- and two-photon microscopy revealed that these dyes showed higher ROS generation ability upon two-photon excitation than upon one-photon excitation via the type I process. The PSs have superior PDT properties compared to conventional Visudyne and 5-ALA under mild conditions. These characteristics allowed for precise PDT at the target region in mimic tumor spheroids, demonstrating that the developed TP PS could be useful in efficient PDT applications and in designing various PSs.Azo containing dyes as a two-photon selective and type I based photosensitizers (PSs) were developed that exhibit excellent photodynamic therapy properties under mild condition. 相似文献
113.
Dong-Dong Zhou Jun Wang Pin Chen Yangyong He Jun-Xi Wu Sen Gao Zhihao Zhong Yunfei Du Dingyong Zhong Jie-Peng Zhang 《Chemical science》2021,12(4):1272
Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H3btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N–H⋯N hydrogen bonds. While the H3btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag3(btim)] coordination networks based on double N–Ag–N bonds at 423 K, by virtue of the unconventional metal–acid replacement reaction (Ag reduces H+). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host–guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(i) coordination network, giving drastically different host–guest recognition behaviours. 相似文献
114.
The binary phase diagram of KNO3-KClO3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO3)1−x(ClO3)x (0<x<0.20) and K(NO3)1−x(ClO3)x (0.90<x<1.0), were formed in the KNO3-based solid solutions and KClO3-based solid solutions phase, respectively. For KNO3-based solid solutions, KNO3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO3 by ClO3-radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO3-based (α) phase and KClO3-based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent. 相似文献
115.
Tadatomi Nishikubo Atsushi Kameyama Jun Yamashita Masao Tomoi Wakichi Fukuda 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):939-947
The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO2) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO2 proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc. 相似文献
116.
117.
Xin Sheng Li Yan Xin Chen Yao Jun Zhang Chun Xin Ji Qin Xin 《Reaction Kinetics and Catalysis Letters》1996,58(2):391-396
Hydrogen adsorption-desorption over Mo2N has been studied using a temperature-programmed technique. It is revealed that hydrogen on Mo2N exhibits very high mobility leading to migration of the surface hydrogen into the sublayer and bulk of the sample or the reverse. The surface hydrogen species are preferentially formed when adsorption is carried out below 573 K. On increasing the adsorption temperature to above 573 K, the quantity of hydrogen species located in the sublayer or/and bulk of the Mo2N sample increases significantly. 相似文献
118.
采用二硫化碳重结晶富勒烯混合物或二硫化碳二次抽提烟灰以提取高富勒烯(higherfulerenes,Cn,n>70)。产物经高效液相色谱分析,高富勒烯的含量从1%分别提高到4%和6%;经激光飞行时间质谱证明,产物中除含主要成分C60和C70以外,还含有C76、C78、C82、C84以及更高碳原子的富勒烯。 相似文献
119.
Zhou S Xu C Wang J Gao W Akhverdiyeva R Shah V Gross R 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):7926-7932
Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees. 相似文献
120.
Most magnetorheological materials, composed of magnetic microparticles in a liquid, require significant amounts of magnetic particles and a large magnetic field to achieve the desired effects. Here, we report on a new type of magnetorheological materials consisting of small amounts of magnetic nanoparticles (0.8 wt %) but exhibiting large rheological change (i.e., a gel-sol transition) upon the application of a small magnetic field. We use self-assembly to create hybrid nanofibers, which consist of supramolecular hydrogelators and magnetic nanoparticles, as the matrices of the hydrogel. Localized in the nanofibers at a distance of 1-2 nm, the magnetic nanoparticles occupy a small volume fraction of the hydrogel, significantly enhancing the magnetic dipole interactions between them, which results in the large magnetoresponse. This strategy generates a hierarchical nanostructure and eliminates several drawbacks of the simple mixture of polymers with nanoparticles, and thus provides a new methodology that uses magnetic force to control the nanostructures and properties of soft materials. 相似文献