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51.
Hideaki Tokuyama Hiroshi Sumida Akifumi Kanehara Susumu Nii 《Colloid and polymer science》2009,287(1):115-121
Stimuli-sensitive porous hydrogels prepared with an emulsion templating method developed by the authors are potentially applicable
in the medical and pharmaceutical fields; thermosensitive N-isopropylacrylamide (NIPA) hydrogels having randomly distributed sphere-like cavities have been prepared by the polymerization
in an aqueous phase in an oil-in-water (O/W) emulsion, followed by the washing of oil (oleyl alcohol) microdroplets. The surfactant
plays a dominant role in the preparation of porous hydrogels and the pore size. This study concerns with the surfactant effects
on the stability of pre-gel O/W emulsions. The porous NIPA hydrogels were successfully prepared using the surfactants forming
the stable emulsion and their internal structures and swelling properties were characterized. The O/W emulsions and the porous
hydrogels prepared using various amounts of oil and surfactant were characterized. The information obtained serves for preparation
of porous hydrogels having suitable porous structure for their applications. 相似文献
52.
New chelating radical ligands pzNNH, pzINH, and pzbisINH (3-pyrazolyl nitronyl nitroxide, 3-pyrazolyl imino nitroxide, and pyrazole-3,5-diyl bis(imino nitroxide), respectively) were prepared. Complexation of these ligands with Ag+ gave [Ag(pzNN)]n, [Ag(pzIN)]6, and [Ag(pzbisIN)]n containing the corresponding anionic forms of the ligands. From the X-ray crystal structure analysis, [Ag(pzIN)]6 was characterized as a dimer of almost planar triangular moieties where the pyrazolate worked as a bridge, and metal-metal bonds brought about dimerization of triangles. [Ag(pzbisIN)]n was characterized as a uniform zigzag chain consisting of pyrazolate bridges and Ag ions with a cis-Npz-Ag-Npz coordination structure. Antiferromagnetic interactions observed could be analyzed based on the structures determined for both compounds. Ferromagnetic coupling was observed in [Ag(pzNN)]n, and a polymeric structure was assumed although the crystal structure could not be determined. Novel supramolecular architectures using pyrazolate-substituted imino nitroxides have been developed, using the unique coordinative versatility of the pyrazolate derivatives 相似文献
53.
Tanaka D Horike S Kitagawa S Ohba M Hasegawa M Ozawa Y Toriumi K 《Chemical communications (Cambridge, England)》2007,(30):3142-3144
Confinement of electron donor guests affords an efficient, photo-induced charge transfer (CT) with the anthracene moieties of a porous coordination polymer. 相似文献
54.
Specific isolation of N-terminal fragments from proteins and their high-fidelity de novo sequencing 总被引:1,自引:0,他引:1
Yamaguchi M Obama T Kuyama H Nakayama D Ando E Okamura TA Ueyama N Nakazawa T Norioka S Nishimura O Tsunasawa S 《Rapid communications in mass spectrometry : RCM》2007,21(20):3329-3336
A new method to determine N-terminal amino acid sequences of multiple proteins at low pmol level by a parallel processing has been developed. The method contains the following five steps: (1) reduction, S-alkylation and guanidination for targeted proteins; (2) coupling with sulfosucccimidyl-2-(biotinamido)ethyl-1,3-dithiopropionate(sulfo-NHS-SS-biotin) to N(alpha)-amino groups of proteins; (3) digestion of the modified proteins by an appropriate protease; (4) specific isolation of N-terminal fragments of proteins by affinity capture using the biotin-avidin system; (5) de novo sequence analysis of peptides by MALDI-TOF-/MALDI-TOF-PSD mass spectrometry with effective utilization of the CAF (chemically assisted fragmentation) method.1 This method is also effective for N-terminal sequencing of each protein in a mixture of several proteins, and for sequencing components of a multiprotein complex. It is expected to become an essential proteomics tool for identifying proteins, especially when used in combination with a C-terminal sequencing method. 相似文献
55.
Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis 总被引:1,自引:0,他引:1
Hasegawa S Horike S Matsuda R Furukawa S Mochizuki K Kinoshita Y Kitagawa S 《Journal of the American Chemical Society》2007,129(9):2607-2614
To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)2.4H2O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)2(NO3)2].6H2O.2DMF}n (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A2. X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled. 相似文献
56.
Mark Kristan Espejo Cabello Dr. Yuta Uetake Dr. Yu Yao Prof. Dr. Susumu Kuwabata Prof. Dr. Hidehiro Sakurai 《化学:亚洲杂志》2021,16(16):2280-2285
An aqueous colloidal dispersion of Pt nanoparticles (NPs) stabilized by fullerenol C60(OH)12 (Pt:C60(OH)12) was successfully synthesized via liquid-phase chemical reduction. The subsequent pyrolysis of Pt:C60(OH)12 at different temperatures was conducted to afford Pt-doped carbon with different chemical compositions (Pt:C60n). X-ray absorption spectroscopy (XAS) and Infrared (IR) absorption spectroscopy and thermogravimetric measurements revealed that the thus-prepared nanocomposite consists of Pt NPs and high valent Pt-C60(OH)12 complex. One distinct feature of C60(OH)12 matrix as catalyst support is the suppression of size growth of Pt NPs during the pyrolysis up to 300 °C. Electrochemical experiments using cyclic voltammetry (CV) and linear sweep voltammetry (LSV) were performed to find that Pt:C60300 (pyrolyzed at 300 °C) exhibited higher activity than others, that was attributed to the π-extended feature of the as-obtained carbon. 相似文献
57.
Osamu Sekiguchi Takuya Masuda Susumu Tajima Nico M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1998,9(10):1029-1034
The metastable decompositions of trimethylsilylmethanol, (CH3)3SiCH2OH (MW: 104, 1) and methoxytrimethylsilane, (CH3)3SiOCH3 (MW: 104, 2) upon electron ionization have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectroscopy and D labeling. The metastable ions of 1 ·+ decompose to give the fragment ions m/z 89 (CH 3 · loss) and 73 (·CH2OH loss), whereas those of 2 ·+ only yield the fragment ion m/z 89 (CH 3 · loss). The latter fragment ion is generated by loss of a methyl radical from the trimethylsilyl group via a simple cleavage reaction as shown by D labeling. However, the fragment ions m/z 89 and 73 from 1 ·+ are generated following an almost statistical exchange of the original methyl and methylene hydrogen atoms in the molecular ion as shown also by D labeling. This exchange indicates a complex rearrangement of the molecular ion of 1 ·+ prior to metastable decomposition for which as key step a 1,2-trimethylsilyl group migration from carbon to oxygen is suggested. A different behavior is also found between the source-generated m/z 89 ions from 1 ·+ which decompose in the metastable time region to give ions m/z 61 by loss of ethylene and those from 2 ·+ which decompose in the metastable region to yield ions m/z 59 by elimination of formaldehyde. 相似文献
58.
Sonomi Arata Dr. Yuna Kim Prof. Norihisa Hoshino Dr. Keishiro Tahara Dr. Kiyonori Takahashi Dr. Tomofumi Kadoya Tomonori Inoue Prof. Takayoshi Nakamura Prof. Tomoyuki Akutagawa Prof. Jun-ichi Yamada Prof. Kazuya Kubo 《欧洲无机化学杂志》2023,26(12):e202300017
Unsymmetrical gold(III)-dithiolene complexes are potential candidates for molecular materials that exhibit thermal structural phase transitions. In this study, unsymmetrical ppy-gold(III) (ppy−=C-deprotonated-2-phenylpyridine(−)) complexes [AuC5] and [AuC6] coordinated by dithiolene ligands containing tetrathiafulvalene (TTF) skeletons with pentylthio (2-{bis(pentylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) and hexylthio groups (2-{bis(hexylthio)-1,3-dithiol-2-ylidene}-1,3-dithiol-4,5-dithiolate(2−)) were synthesized. Both complexes exhibited a large absorption band at approximately 508 nm, owing to intramolecular ligand-to-ligand charge transfer. One-dimensional columnar structures with head-to-tail molecular arrangements around the metal ions were constructed in the crystals. The flexible alkylthio groups were intercalated into crystalline spaces between dithiolene ligands in the columns. [AuC5] exhibits a simple phase transition at 198 °C between crystalline and isotropic phases irreversibly. The crystalline phase of [AuC6] observed at 25 °C melted at 148 °C. Another crystalline phase grew above 148 °C with a very slow crystallization rate from the liquid phase and was completely transformed into an isotropic phase at 200 °C. 相似文献
59.
Iwasaki Y Matsui R Suzuki T Nakazaki A Kobayashi S 《Chemical & pharmaceutical bulletin》2011,59(4):522-524
We have developed a high-yielding and stereoselective vinylogous Mukaiyama aldol reaction (VMAR) of α-haloenals. Contrary to the simple α,β-unsaturated aldehyde, α-haloenals were found to be reactive affording the corresponding VMAR adducts in excellent yields. Some transformations of VMAR adducts by Pd-mediated cross-coupling were also examined in order to demonstrate the synthetic utility of VMAR of α-haloenals. 相似文献
60.
Ohtani R Yoneda K Furukawa S Horike N Kitagawa S Gaspar AB Muñoz MC Real JA Ohba M 《Journal of the American Chemical Society》2011,133(22):8600-8605
Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration. 相似文献