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41.
Guido F. Smits Maarten C. Krol Pieter N. Van Kampen Cornelis Altona 《Journal of Molecular Structure》1986,139(3-4):247-253
Contrary to expectation, the gauche conformer of 1,2-difluoroethane is more stable than the trans conformer in the gas phase. In order to understand the underlying causes of the “gauche effect”, a complete geometry relaxation was performed for the gauche and trans conformers of 1,2-difluoroethane with the 4-21G, 4-31G and 4-31G** basis sets. The 4-31G** optimized geometry of the gauche conformer compares well with the experimental values obtained from a number of electron-diffraction studies. A correction for the correlation energy, calculated by means of second-order Møller—Plesset perturbation theory with the 6-31G** basis set, proves to be essential to obtain a correct estimate of the energy difference between the gauche and trans conformers 1,2-difluoroethane. 相似文献
42.
Bisphenol A polycarbonate degrades due to sunlight, humidity and oxygen. In this study two possible techniques to stabilize the polymer were compared, i.e. blending of UV-absorbers (UVAs) into the polymer or using block copolymers based on resorcinol polyarylates. Combination of different analysis techniques shows that the protection by UVAs is not as good as by the resorcinol polyarylate block copolymers. The block copolymer rearranges itself through a photo-Fries rearrangement within hours into a UV-absorbing top layer. Two different block compositions were studied, and the copolymer with the highest concentration of resorcinol polyarylate groups shows the best protection. 相似文献
43.
Pieter Samyn Jürgen Van ErpsHugo Thienpont Gustaaf Schoukens 《Applied Surface Science》2011,257(13):5613-5625
Papers have a complex hierarchical structure and the end-user functionalities such as hydrophobicity are controlled by a finishing layer. The application of an organic nanoparticle coating and drying of the aqueous dispersion results in an unique surface morphology with microscale domains that are internally patterned with nanoparticles. Better understanding of the multi-scale surface roughness patterns is obtained by monitoring the topography with non-contact profilometry (NCP) and atomic force microscopy (AFM) at different sampling areas ranging from 2000 μm × 2000 μm to 0.5 μm × 0.5 μm. The statistical roughness parameters are uniquely related to each other over the different measuring techniques and sampling sizes, as they are purely statistically determined. However, they cannot be directly extrapolated over the different sampling areas as they represent transitions at the nano-, micro-to-nano and microscale level. Therefore, the spatial roughness parameters including the correlation length and the specific frequency bandwidth should be taken into account for each measurement, which both allow for direct correlation of roughness data at different sampling sizes. 相似文献
44.
Sytze J. Buwalda Pieter J. Dijkstra Jan Feijen 《Journal of polymer science. Part A, Polymer chemistry》2012,50(9):1783-1791
The aqueous solution behavior and thermoreversible gelation properties of pyridine‐end‐functionalized poly(ethylene glycol)–poly(L ‐lactide) (PEG–(PLLA)8–py) star block copolymers in the presence of coordinating transition metal ions were studied. In aqueous solutions, the macromonomers self‐assembled into micelles and micellar aggregates at low concentrations and formed physically crosslinked, thermoreversible hydrogels above a critical gel concentration (CGC) of 8% w/v. In the presence of transition metal ions like Cu(II), Co(II), or Mn(II), the aggregate dimensions increased. Above the CGC, the gel–sol transition shifted to higher temperatures due to the formation of additional crosslinks from intermolecular coordination complexes between metal ions and pyridine ligands. Furthermore, as an example, PEG–(PLLA)8–py hydrogels stabilized by Mn(II)–pyridine coordination complexes were more resistant against degradation/dissolution when placed in phosphate buffered saline at 37 °C when compared with hydrogels prepared in water. Importantly, the stabilizing effect of metal–ligand coordination was noticeable at very low Cu(II) concentrations, which have been reported to be noncytotoxic for fibroblasts in vitro. These novel PEG–(PLLA)8–py metallo‐hydrogels, which are the first systems to combine metal–ligand coordination with the advantageous properties of PEG–PLLA copolymer hydrogels, are appealing materials that may find use in biomedical as well as environmental applications like the removal of heavy metal ions from waste streams. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
45.
Air-coupled ultrasound (ACU) provides a tool to evaluate wood samples of small or moderate thickness (<30 mm) thereby avoiding direct contact or liquid coupling. Results of through-transmission ACU measurements on wood veneer samples and related products are reported with respect to a wide variety of quality aspects. Fluctuations in the averaged received signal levels appear to be correlated to the presence of natural or machine-induced thickness and density variations, flaws and grain damage, errors produced by the manufacturing process, insufficient bonding on a substrate, etc. In addition it is seen that the variability of the signal levels enables to distinguish between quarter and crown areas. 相似文献
46.
47.
Samyn P Schoukens G Vonck L Stanssens D Van den Abbeele H 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):8509-8521
Celluloses are preferred renewable substrates, but hydrophilicity and porosity disfavor their water resistance. We present here an ecofriendly application of imidized nanoparticles and a method to flexibly tune the surface wettability of papers. The soft nanostructured coating is sensitive to thermal curing, which affects both the surface chemistry and morphology. The thermal stability of the coating is first investigated with conventional and modulated differential scanning calorimetry, revealing influences of the imide content and an endotherm reaction below the glass transition temperature at 120-150 °C. The latter is studied in detail for an appropriate selection of the copolymer precursors. According to diffuse reflection infrared spectroscopy, Raman spectroscopy, and UV/vis spectroscopy, the endotherm corresponds to an imidization reaction. The morphology of the coatings is followed at various scale levels by contactless roughness measurements and atomic force microscopy. Finally, the experimental values are fitted to the parameters of the Wenzel wetting model, and so-called calibration curves for the relation between contact angles, surface roughness, and surface chemistry are presented. They allow the prediction of the water contact angle of coated papers from the hydrophilic to the hydrophobic range, with a maximum in hydrophobicity after increasing the imide content at 120-150 °C curing. 相似文献
48.
Zhou Q Ristenpart WD Stroeve P 《Langmuir : the ACS journal of surfaces and colloids》2011,27(19):11747-11751
We report a magnetic technique for altering the apparent contact angle of aqueous droplets deposited on a nanostructured surface. Polymeric tubes with embedded superparamagnetic magnetite (Fe(3)O(4)) nanoparticles were prepared via layer-by-layer deposition in the 800 nm diameter pores of polycarbonate track-etched (PCTE) membranes. Etching away the original membrane yields a superparamagnetic film composed of mostly vertical tubes attached to a rigid substrate. We demonstrate that the apparent contact angle of pure water droplets deposited on the nanostructured film is highly sensitive to the ante situm strength of an applied magnetic field, decreasing linearly from 117 ± 1.3° at no applied field to 105 ± 0.4° at an applied field of approximately 500 G. Importantly, this decrease in contact angle did not require an inordinately strong magnetic field: a 15° decrease in contact angle was observed even with a standard alnico bar magnet. We interpret the observed contact angle behavior in terms of magnetically induced conformation changes in the film nanostructure, and we discuss the implications for reversibly switching substrates from hydrophilic to hydrophobic via externally tunable magnetic fields. 相似文献
49.
Thao Do Thi Koen Nauwelaerts Luc Baudemprez Michiel Van Speybroeck Jan Vermant Patrick Augustijns Pieter Annaert Johan Martens Jan Van Humbeeck Guy Van den Mooter 《Journal of inclusion phenomena and macrocyclic chemistry》2011,71(1-2):137-147
Complexation in solution between danazol and two different cyclodextrins [2-hydroxypropyl-??-cyclodextrin (HP-??-CD) and 2-hydroxypropyl-??-cyclodextrin (HP-??-CD)] was studied using phase solubility analysis, and one- and two-dimensional 1H-NMR. The increase of danazol solubility in the aqueous cyclodextrin solutions showed a linear relationship (AL profile). The apparent stability constant, K 1:1, of each complex was calculated and found to be 51.7 × 103 and 7.3 × 103 M?1 for danazol?CHP-??-CD and danazol?CHP-??-CD, respectively. 1H-NMR spectroscopic analysis of varying ratios of danazol and the different cyclodextrins in a mixture of EtOD?CD2O confirmed the 1:1 stoichiometry. Cross-peaks, from 2D ROESY 1H-NMR spectra, between protons of danazol and H3?? and H5??of cyclodextrins, which stay inside the cyclodextrin cavity, proved the formation of an inclusion complex between danazol and the cyclodextrins. For HP-??-CD, the inclusion complex is formed by entrance of the isooxazole and the A rings of danazol in the cyclodextrin cavity. For HP-??-CD, two different inclusion structures may exist simultaneously in solution: one with the isooxazole and A ring in the cavity and the other with the C and D ring inside the cavity. DLS showed that self-aggregation of the CD??s was absent in the danazol HP-??-CD system up to a CD concentration of 10% and in the danazol HP-??-CD system up to a CD concentration of 5%. 相似文献
50.
Blaise Mavinga MbalaJan Jacobs Pieter ClaesVirima Mudogo Norbert De Kimpe 《Tetrahedron》2011,67(45):8747-8756
As part of our research on 2-aza analogues of pentalongin, the active principle of Pentas longiflora Oliv., the first synthesis of 2,3-disubstituted benzo[g]isoquinoline-1,5,10(2H)-triones via 3,4-disubstituted 6-hydroxybenzo[g]furo[4,3,2-de]isoquinoline-2,5(4H)-diones as the key intermediates is reported. The latter compounds have been prepared by treating 2-methoxycarbonyl-1,4-naphthoquinone with N-substituted enaminoesters under acidic conditions. These reagents are easily accessible from readily available 1,4-dihydroxy-2-naphthoic acid, β-ketoesters and primary amines. Finally, a short synthesis of substituted benzo[g]isoquinoline-1,5,10(2H)-triones is achieved by an oxidative addition of N-substituted enaminoesters onto methyl 1,4-dihydroxynaphthalene-2-carboxylate. 相似文献