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31.
Terrence G. Vargo Daniel J. Hook Joseph A. Gardella Mary A. Eberhardt Anne E. Meyer Robert E. Baier 《Journal of polymer science. Part A, Polymer chemistry》1991,29(4):535-545
Recent work in our laboratories has fully characterized the surface region of a segmented poly(ether-urethane) (PEU) extending from the air/polymer interfacial region through bulk depths in the micron range. This characterization utilized energy and angle dependent Electron Spectroscopy for Chemical Analysis (ESCA), Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy (ATR–FTIR), and Comprehensive Wettability Profiling (contact angle using a homologous series of liquids) as defined by Zisman. In this study this same multi-analytical-technique approach is used to elucidate changes in these PEU surfaces induced through an H2O Radio Frequency Glow Discharge (RFGD) plasma. This investigation reports both qualitative and quantitative changes due to the modification treatments as well as the permanency of the changes effected on these surfaces through the plasma treatment. From our analyses, the amount of surface residing polyurethane (hard segment) is observed to increase due to a proposed plasma etching mechanism. Further, the addition of oxygen containing functionality is detected at the modified surfaces unique with respect to the unmodified PEU. These surface modifications which show large increases in wettability, are finally observed to be semi-permanent over a time period of 6 months. 相似文献
32.
Anders Thygesen Jette Oddershede Hans Lilholt Anne Belinda Thomsen Kenny Ståhl 《Cellulose (London, England)》2005,12(6):563-576
A comparative study of cellulose crystallinity based on the sample crystallinity and the cellulose content in plant fibres
was performed for samples of different origin. Strong acid hydrolysis was found superior to agricultural fibre analysis and
comprehensive plant fibre analysis for a consistent determination of the cellulose content. Crystallinity determinations were
based on X-ray powder diffraction methods using side-loaded samples in reflection (Bragg-Brentano) mode. Rietveld refinements
based on the recently published crystal structure of cellulose Iβ followed by integration of the crystalline and amorphous
(background) parts were performed. This was shown to be straightforward to use and in many ways advantageous to traditional
crystallinity determinations using the Segal or the Ruland–Vonk methods. The determined cellulose crystallinities were 90–100 g/100 g
cellulose in plant-based fibres and 60–70 g/100 g cellulose in wood based fibres. These findings are significant in relation
to strong fibre composites and bio-ethanol production. 相似文献
33.
Franzén J Marigo M Fielenbach D Wabnitz TC Kjaersgaard A Jørgensen KA 《Journal of the American Chemical Society》2005,127(51):18296-18304
The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts. 相似文献
34.
Andrea Cornia Antonio Costantino Fabretti Roberta Sessoli Lorenzo Sorace Dante Gatteschi Anne‐Laure Barra Carole Daiguebonne Thierry Roisnel 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m371-m373
The structure of hexadeca‐μ‐acetato‐tetraaquadodeca‐μ3‐oxo‐dodecamanganese bis(acetic acid) tetrahydrate, [Mn12O12(CH3COO)16(H2O)4]·2CH3COOH·4H2O, known as Mn12–acetate, has been determined at 83 (2) K by X‐ray diffraction methods. The fourfold (S4) molecular symmetry is disrupted by a strong hydrogen‐bonding interaction with the disordered acetic acid molecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn12 isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen‐bonded acetic acid molecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B 36 , 2042–2046]. 相似文献
35.
A method for fast in situ measurement of adsorption kinetics based on a finite bath was developed. We modified the conventional finite bath by replacing the external loop by a dip probe which enables in situ measurement of the concentration change in the contactor. Deposition of adsorbent particles on the reflection surface of the dip probe compromised measurements. Different membranes, a polyamide, a polypropylene and a nylon membrane were tested to protect the internal reflection surface of the dip probe from fouling with adsorbent particles. The nylon membrane provided efficient protection and high mass transfer evaluated by response time experiments. Unspecific adsorption of the model protein on the membrane could also be excluded. To corroborate the measurements of the dip probe the results were compared to a conventional finite bath and to a shallow-bed. The uptake curves for human polyclonal IgG at different concentrationes (0.1-3 g/l) on rProtein A Sepharose FF and MabSelect were used as model system. The effective diffusion coefficients were determined using a pore diffusion model. These values were in good agreement for all methods. 相似文献
36.
Top S Vessières A Leclercq G Quivy J Tang J Vaissermann J Huché M Jaouen G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(21):5223-5236
A series of ferrocene derivatives based upon the structure of the antiestrogenic drug tamoxifen or of its active metabolite hydroxytamoxifen has been prepared and named by analogy ferrocifens and hydroxyferrocifens. This series includes 1-[4-(O(CH(2))(n)NMe(2))phenyl]-1-phenyl-2-ferrocenyl-but-1-ene and 1-[4-(-O(CH(2))(n)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene, with n=2, 3, 5 and 8, and 1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenylethene. Most of these molecules have been synthesised by McMurry cross-coupling of the appropriate ketones, except for the ethene complexes, which were prepared by a four-step reaction sequence starting from the ferrocenylacetic acid. All these compounds were obtained as mixtures of Z and E isomers. The isomers were separated in the cases of the ferrocenyl derivatives of tamoxifen and hydroxytamoxifen (n=2). No isomerisation of the Z and E isomers occurred in DMSO after one day, while a 50:50 mixture of the isomers was obtained within one hour in chloroform. The X-ray structure of (E)-1-[4-(-O(CH(2))(2)NMe(2))phenyl]-1-(4-hydroxyphenyl)-2-ferrocenyl-but-1-ene has been determined. The relative binding affinity (RBA) values of the hydroxyferrocifens for the estrogen receptor alpha (ERalpha) was good to moderate, with values decreasing progressively with the length of the basic chain. The RBA values found for the estrogen receptor beta (ERbeta) are equal to or slightly less than those found for the alpha form. The lipophilicity of the hydroxyferrocifens are superior to the values found for estradiol and increase with lengthening of the chain. The antiproliferative effects of the four hydroxyferrocifens with n=2, 3, 5 and 8 were studied on four breast cancer cell lines (MCF7, MDA-MB231, RTx6 and TD5) possessing different levels of ERalpha. On MCF7 cells containing high levels of ERalpha, hydroxyferrocifens behave as antiestrogens. At a molarity of 1 microM the effect is close to that of hydroxytamoxifen (used for reference) when n=2 or 5, more marked when n=3, and weaker when n=8. Ferrocene alone has no effect. For the MDA-MB231 cells, classed as a hormone-independent breast cancer cell line, on the other hand, the hydroxyferrocifens show remarkable antiproliferative behaviour while the hydroxytamoxifen is completely inactive. Hydroxyferrocifens therefore show the unique property of being active both on hormone-dependent and on hormone-independent breast cancer cell lines. The molecular modelling study provides some clues for understanding of the antagonist effect of these molecules, while an additional cytotoxic effect due to the vectorised ferrocenyl unit is revealed in some occasions. 相似文献
37.
Theodorus J.M. de Bruin Karoly Vekey Yves Gimbert Anne Milet 《Journal of organometallic chemistry》2006,691(20):4281-4288
The influence of carbon-carbon triple bond polarization on the regiochemistry of the Pauson-Khand reaction has been studied with the B3LYP functional. The regiochemistry determining step of this reaction, i.e., olefin insertion leading to cobaltacycle formation, has been examined with ethylene as the olefin and propyne, methyl 2-butynoate, and methyl propiolate as the acetylenes. From this study, it has been concluded that, in absence of overwhelming steric effects of an acetylene substituent, the regiochemistry is influenced by the polarization of the acetylenic bond, which arises from the different substituents. The initial C-C bond is preferentially formed with the acetylenic carbon that has the greater electron density: with propyne, this leads to a cyclopentenone having the methyl group in the α-position; with methyl 2-butynoate, to a cyclopentenone with the CO2Me in the β-position; with methyl propiolate, which is virtually unpolarized in the complex, to a cyclopentenone with the CO2Me in the α-position (a result of steric effects). These theoretical results are concordant with those observed experimentally with norbornene. The question of axial versus equatorial reactive positions for the coordinated olefin is also addressed and a kinetic simulation is presented. 相似文献
38.
The formation region of the various types of layered titanium hydrogen phosphate hydrates was investigated. The materials were prepared by hydrothermal methods, treating amorphous titanium phosphate with phosphoric acid (8 to 16M) in the temperature range 175 to 250°C. The materials obtained were:α-Ti(HPO4)2·H2O,γ-Ti(PO4)(H2PO4)·2H2O, and its anhydrous formβ-Ti(PO4)(H2PO4). The structure ofβ-Ti(PO4)(H2PO4) has been determined by Rietveld powder refinement of high resolution neutron diffraction data. The structure is refined in the monoclinic space groupP21/n(No. 14). The unit cell parameters are:a=18.9503(4) Å,b=6.3127(1) Å,c=5.1391(1) Å,β=105.366(2)°;Z=4. The final agreement factors were:Rp=2.9% andRwp=3.8%. The structure ofβ-Ti(PO4)(H2PO4) is built from TiO6octahedra linked together by tertiary phosphate (PO4) and dihydrogen phosphate ((OH)2PO2) tetrahedra. The layers are held together by hydrogen bonds. 相似文献
39.
Galan MC Venot AP Glushka J Imberty A Boons GJ 《Journal of the American Chemical Society》2002,124(21):5964-5973
It is demonstrated that conformationally restricted oligosaccharides can act as acceptors for glycosyltransferases. Correlation of the conformational properties of N-acetyl lactosamine (Galbeta(1-4)GlcNAc, LacNAc) and several preorganized derivatives with the corresponding apparent kinetic parameters of rat liver alpha-(2,6)-sialyltransferase-catalyzed sialylations revealed that this enzyme recognizes LacNAc in a low energy conformation. Furthermore, small variations in the conformational properties of the acceptors resulted in large differences in catalytic efficiency. Collectively, our data suggest that preorganization of acceptors in conformations that are favorable for recognition by a transferase may improve catalytic efficiencies. 相似文献
40.
The effects of adding millimolar quantities of a series of compounds containing the carbonyl function on the conductances of solutions (0.2 mM) of tri-n-butylammonium picrate ino-dichlorobenzene solvent at 25°C have been measured. Values of the complex formation constants K
1
+
for 1:1 cation-ligand complexes are derived from these data. The corresponding values of –G
1
0
at 25°C are (in kcal-mole
–1
): 4-butyrolactone, 4.29; propylene carbonate, 3.87; ethylene carbonate, 3.59; cyclopentanone, 3.42; ethyl acetate, 2.84; and diethyl carbonate, 2.78. These results together with earlier results from this laboratory are discussed in terms of the effects of structure on cation-ligand affinity. 相似文献