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201.
Luiz Claudio de Santa Maria Mônica R.M.P Aguiar Marcia C.V Amorim Raphael S.M Almeida Ana J.B Oliveira 《European Polymer Journal》2003,39(2):291-296
A series of porous copolymer beads based on methacrylamide (MA), styrene and divinylbenzene (DVB) was prepared by aqueous suspension polymerization in the presence of diluents to act as precipitants. As MA is totally soluble into aqueous phase, the use of two types of phase transfer agent was investigated, namely: TritonX-100TM [polyoxyethylene-(10)-isooctylphenyl-ether] and tetrabutylammonium perchlorate. The effect of the diluents on the surface appearance and the porous structure of copolymer beads was studied. Suitable particle stabilisation was achieved by using a combination of two suspension agents, namely: gelatin and 2-hydroxy-ethyl-cellulose. The network resins were characterized by optical and scanning electron microscopy, IR spectroscopy, elemental analysis (CHN), apparent density, swelling in different solvents and specific area by BET method. It was observed that the MA incorporation was more effective when TritonTM was employed as phase transfer agent. 相似文献
202.
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204.
Silva SS Maniglio D Motta A Mano JF Reis RL Migliaresi C 《Macromolecular bioscience》2008,8(8):766-774
Nanometric silk-fibroin nets were fabricated by electrospinning from regenerated Bombyx mori silk-fibroin (SF)/formic acid solutions with the addition of genipin (GE), 2, 15 and 24 h after the solution preparation. After spinning, the pure fibroin nanofibers were water soluble and needed a further stabilization process, whereas the reaction of fibroin with genipin resulted in water-insoluble fibroin nets due to conformational changes induced in the fibroin by the genipin. SFGE nanofibers presented diameters ranging from 140 to 590 nm and were generally thinner than pure SF nanofibers. The secondary structure of SF into SFGE nanofibers showed the presence of a beta-sheet conformation together with beta-turn intermediates (turns and bends). The approach described in this paper provides an alternative method of designing SF nanofibers that are already water insoluble, without any stability post-treatment needed. 相似文献
205.
Silk fibroin from Bombyx mori is a high-molecular-weight protein, largely employed in the biomaterials field. Several parameters can affect the folding and assembly of fibroin heavy and light chains. The present work has shown that anisotropic and water-stable films are produced when fibroin solution is cast under an alternating electric field (AC). The treatment can affect the mechanical, thermal and surface properties of fibroin films. These effects have been related to the alignment of molecular dipoles and the formation of oriented supramolecular assemblies. Cell response is affected by this novel processing: MRC5 fibroblasts, cultured on anisotropic fibroin films, preferentially spread parallel to the field direction 6 h after seeding. [Figure: see text]. 相似文献
206.
Miyata K Mineo R Tamamushi R Mizuta M Ohkubo A Taguchi H Seio K Santa T Sekine M 《The Journal of organic chemistry》2007,72(1):102-108
New bi- and tricyclic deoxycytidine derivatives (dChpd, dCmpp, dCtpp, dCppp) were synthesized as analogues of a fluorescent nucleoside, dChpp, previously reported. The carbamoyl group of dChpd and the 5-position of the cytosine ring are bridged via an ethylene linker so that the modified group forms a nonplanar structure with the cytosine ring. The fluorescent study of dChpd indicated that the coplanar structure between the carbamoyl group and the cytosine ring is of importance. N-Methylation of the carbamoyl group (dCmpp) weakened the intensity of the fluorescence of dChpp, and the derivative (dCtpp), which had a thiocarbamoyl group, lost its fluorescent property. Moreover, addition of a pyrrolo-ring (dCppp) to dChpp enhanced the intensity of fluorescence, and an emission light was observed with a marked Stokes shift of 120 nm. 相似文献
207.
Claramunt RM María DS Pinilla E Torres MR Elguero J 《Molecules (Basel, Switzerland)》2007,12(9):2201-2214
2-(2,4-Dimethylphenyl)-2H-benzotriazole (1) has been synthesized in a three step procedure starting from 2,4-dimethyl-N-(2-nitrophenyl)benzamide via a 5-(2,4- dimethylphenyl)-1-(2-nitrophenyl)-1H-tetrazole intermediate. Its structure and those of Tinuvin P and 2-phenyl-2H-benzotriazole (5) have been studied by multinuclear NMR (1H-, 13C- and 15N-) in solution and in the solid state. X-ray diffraction analysis of 1 and 5 allowed to us establish the molecular conformation around the single bond connecting the two aromatic systems, in agreement with the conclusions drawn from the NMR study. In the case of 1 ab initio geometry optimization was achieved at the Hartree-Fock HF/6- 31G** and DFT B3LYP/6-31G** levels. 相似文献
208.
Al-Dirbashi OY Santa T Al-Qahtani K Al-Amoudi M Rashed MS 《Rapid communications in mass spectrometry : RCM》2007,21(13):1984-1990
We describe a new approach applicable to the determination of organic acids that serve as diagnostic markers for several inherited metabolic disorders. We utilized liquid chromatography/tandem mass spectrometry for analysis of organic acid derivatives of a recently described benzofurazan reagent. The derivatization step was necessary to obtain organic acid derivatives suitable for analysis by reversed-phase liquid chromatography with high ionization efficiency for mass spectrometry in the positive-ion mode. In this work, a group of related dicarboxylic acid markers containing five or six carbon atoms were analyzed and validation was performed for glutaric and 3-hydroxyglutaric acids, the specific markers for glutaric acidemia type 1. Derivatization was achieved by reacting untreated urine with the derivatization reagent under mild conditions. The reaction mixture was analyzed on a C18 ultra-performance liquid chromatography (UPLC) column (50x2.1 mm, 1.7 microm) and detected in the multiple reaction monitoring mode in 5 min. Calibration curves were linear up to at least 1000 microM with detection limits for glutaric and 3-hydroxyglutaric acids of 0.025 and 0.02 microM, respectively (signal-to-noise ratio of 3). Intra-day (n=11) and inter-day (n=6) coefficients of variation were better than 11.2%. The assay was successfully applied to control (n=134) and glutaric acidemia type 1 (n=55) urine samples. 相似文献
209.
Uldry AC Griffin JM Yates JR Pérez-Torralba M María MD Webber AL Beaumont ML Samoson A Claramunt RM Pickard CJ Brown SP 《Journal of the American Chemical Society》2008,130(3):945-954
Weak hydrogen bonding in uracil and 4-cyano-4'-ethynylbiphenyl, for which single-crystal diffraction structures reveal close CH...O=C and C[triple bond]CH...N[triple bond]C distances, is investigated in a study that combines the experimental determination of 1H, 13C, and 15N chemical shifts by magic-angle spinning (MAS) solid-state NMR with first-principles calculations using plane-wave basis sets. An optimized synthetic route, including the isolation and characterization of intermediates, to 4-cyano-4'-ethynylbiphenyl at natural abundance and with 13C[triple bond]13CH and 15N[triple bond]C labeling is described. The difference in chemical shifts calculated, on the one hand, for the full crystal structure and, on the other hand, for an isolated molecule depends on both intermolecular hydrogen bonding interactions and aromatic ring current effects. In this study, the two effects are separated computationally by, first, determining the difference in chemical shift between that calculated for a plane (uracil) or an isolated chain (4-cyano-4'-ethynylbiphenyl) and that calculated for an isolated molecule and by, second, calculating intraplane or intrachain nucleus-independent chemical shifts that quantify the ring current effects caused by neighboring molecules. For uracil, isolated molecule to plane changes in the 1H chemical shift of 2.0 and 2.2 ppm are determined for the CH protons involved in CH...O weak hydrogen bonding; this compares to changes of 5.1 and 5.4 ppm for the NH protons involved in conventional NH...O hydrogen bonding. A comparison of CH bond lengths for geometrically relaxed uracil molecules in the crystal structure and for geometrically relaxed isolated molecules reveals differences of no more than 0.002 A, which corresponds to changes in the calculated 1H chemical shifts of at most 0.1 ppm. For the C[triple bond]CH...N[triple bond]C weak hydrogen bonds in 4-cyano-4'-ethynylbiphenyl, the calculated molecule to chain changes are of similar magnitude but opposite sign for the donor 13C and acceptor 15N nuclei. In uracil and 4-cyano-4'-ethynylbiphenyl, the CH hydrogen-bonding donors are sp2 and sp hybridized, respectively; a comparison of the calculated changes in 1H chemical shift with those for the sp3 hybridized CH donors in maltose (Yates et al. J. Am. Chem. Soc. 2005, 127, 10216) reveals no marked dependence on hybridization for weak hydrogen-bonding strength. 相似文献
210.
M. Motta C. V. Deimling M. J. Saeki P. N. Lisboa-Filho 《Journal of Sol-Gel Science and Technology》2008,46(2):201-207
Several routes and procedures have been used in these last years as an effort to achieve single-phase mesoscopic-size superconducting
samples. In this paper, the effects of using citric acid (CA), tartaric acid (TA) and ethylenediaminetetraacetic acid (EDTA)
as chelating agents and ethylene-glycol (EG) as polyhydroxy alcohol were studied in order to establish conditions to avoid
the occurrence of BaCO3 undesirable secondary phase in YBa2Cu3O7−δ (YBCO). Thermal evolution of intermediate compounds formed during the calcinations process by the use of different chelating
agents was traced using thermogravimetric and spectroscopic methods. The obtained results indicated that the polymer breakdown
of samples prepared using EDTA occurs at higher temperatures than others chelating agents and also reduces the occurrence
of BaCO3 secondary phase as studied by X-ray diffraction measurements. Furthermore, the magnetic response of the mesoscopic-size YBCO
specimens obtained was verified showing that samples present different superconducting response. 相似文献