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71.
In this work, a parallel pore model (PPM) and a pore network model (PNM) are developed to provide a state-of-art method for the calculation of several characteristic pore structural parameters from inverse size-exclusion chromatography (ISEC) experiments. The proposed PPM and PNM could be applicable to both monoliths and columns packed with porous particles. The PPM and PNM proposed in this work are able to predict the existence of the second inflection point in the experimental exclusion curve that has been observed for monolithic materials by accounting for volume partitioning of the polymer standards in the macropores of the column. The appearance and prominence of the second inflection point in the exclusion curve is determined to depend strongly on the void fraction of the macropores (flow-through pores), (b) the nominal diameter of the macropores, and (c) the radius of gyration of the largest polymer standard employed in the determination of the experimental ISEC exclusion curve. The conditions that dictate the appearance and prominence of the second inflection point in the exclusion curve are presented. The proposed models are applied to experimentally measured ISEC exclusion curves of six silica monoliths having different macropore and mesopore diameters. The PPM and PNM proposed in this work are able to determine the void fractions of the macropores and silica skeleton, the pore connectivity of the mesopores, as well as the pore number distribution (PND) and pore volume distribution (PVD) of the mesopores. The results indicate that the mesoporous structure of all materials studied is well connected as evidenced by the similarities between the PVDs calculated with the PPM and the PNM, and by the high pore connectivity values obtained from the PNM. Due to the fact that the proposed models can predict the existence of the second inflection point in the exclusion curves, the proposed models could be more applicable than other models for ISEC characterization of chromatographic columns with small diameter macropores (interstitial pores) and/or large macropore (interstitial pore) void fractions. It should be noted that the PNM can always be applied without the use of the PPM, since the PPM is an idealization that considers an infinitely connected porous medium and for materials having a low (<6) pore connectivity the PPM would force the PVD to a lower average diameter and larger distribution width as opposed to properly accounting for the network effects present in the real porous medium. 相似文献
72.
M. Ramm M. Ata T. Gross W. Unger 《Applied Physics A: Materials Science & Processing》2000,70(4):387-390
We report core-level and valence-band X-ray photoelectron spectroscopy (XPS) and carbon [
]K near-edge X-ray-absorptionfine structure spectroscopy (NEXAFS) results of plasma-polymerized C60. In comparison with evaporated C60 the C 1s peak is broader and asymmetric for the C60 polymer and its shake-up satellites diminished. Furthermore, the features of the valence-band as well as the features of
the π* antibonding orbitals of the C60 polymer are broader and reduced in intensity. Changes in the electronic structure are attributed to the polymerization of
C60, the post-plasma functionalization of the surface by oxygen after exposure to atmosphere, and the occurrence of amorphous
carbon.
Received: 28 May 1999 / Accepted: 31 August 1999 / Published online: 8 March 2000 相似文献
73.
In this study, methanol extracts (MEs) and essential oil (EO) of Angelica purpurascens (Avé-Lall.) Gill obtained from different parts (root, stem, leaf, and seed) were evaluated in terms of antioxidant activity, total phenolics, compositions of phenolic compound, and essential oil with the methods of 2,2-azino-bis(3ethylbenzo-thiazoline-6-sulfonic acid (ABTS•+), 2,2-diphenyl-1-picrylhydrazil (DPPH•) radical scavenging activities, and ferric reducing/antioxidant power (FRAP), the Folin–Ciocalteu, liquid chromatography−tandem mass spectrometry (LC−MS/MS), and gas chromatography-mass spectrometry (GC−MS), respectively. The root extract of A. purpurascens exhibited the highest ABTS•+, DPPH•, and FRAP activities (IC50: 0.05 ± 0.0001 mg/mL, IC50: 0.06 ± 0.002 mg/mL, 821.04 ± 15.96 µM TEAC (Trolox equivalent antioxidant capacity), respectively). Moreover, EO of A. purpurascens root displayed DPPH• scavenging activity (IC50: 2.95 ± 0.084 mg/mL). The root extract had the highest total phenolic content (438.75 ± 16.39 GAE (gallic acid equivalent), µg/mL)). Twenty compounds were identified by LC−MS/MS. The most abundant phenolics were ferulic acid (244.39 ± 15.64 μg/g extract), benzoic acid (138.18 ± 8.84 μg/g extract), oleuropein (78.04 ± 4.99 μg/g extract), and rutin (31.21 ± 2.00 μg/g extract) in seed, stem, root, and leaf extracts, respectively. According to the GC−MS analysis, the major components were determined as α-bisabolol (22.93%), cubebol (14.39%), α-pinene (11.63%), and α-limonene (9.41%) among 29 compounds. Consequently, the MEs and EO of A. purpurascens can be used as a natural antioxidant source. 相似文献
74.
David J. Unger 《Journal of Elasticity》2014,117(2):139-161
An analytical technique is developed that reduces the unknown elastic-plastic boundary of a linear elastic-perfectly plastic material containing an elliptical hole under tensile plane stress loading conditions into an equivalent mathematical problem with known boundaries. This mathematical transformation may facilitate this problem’s solution by either analytical or numerical means. Yield is assumed to occur in this analysis under the Tresca yield criterion. An example elastic-plastic problem illustrating this method is drawn from existing literature in the form of a perturbation solution for an elliptical hole derived by a series expansion about a circular boundary. 相似文献
75.
A brief historical survey is presented on the evaluation of silica adsorbents in analytical HPLC. The theory of analytical HPLC is mostly still being based on the height equivalent to a theoretical plate concept and the van Deemter equation that was derived from gas phase adsorption involving a linear adsorption isotherm and fast mass transfer kinetics. One can obviously wonder whether the use of the van Deemter equation is relevant and valid for the evaluation of the performance of HPLC systems, where most often the liquid solutes involve charged molecules in electrolytes and in very many cases the adsorbates are macromolecules having diffusion coefficients of small magnitude. Instead of the van Deemter equation, a multi-scale modelling approach that involves microscopic and macroscopic dynamic non-linear mass-transfer-rate models should be employed. Furthermore, advanced experimental methods for the characterisation of porous media and the distribution of the density of immobilised active sites (e.g., ligands) on surfaces as well as microscopic pore-network modelling and molecular dynamics modelling and simulation methods could be used for the design of novel adsorbents whose porous structures and immobilised active sites would provide effective mass transport and adsorption rates for realising efficient separations as well as high dynamic capacities when larger throughputs are required. 相似文献
76.
Traulsen CH Darlatt E Richter S Poppenberg J Hoof S Unger WE Schalley CA 《Langmuir : the ACS journal of surfaces and colloids》2012,28(29):10755-10763
Aiming at the functionalization of surfaces with terpyridine anchors for the coordinative deposition of additional layers, mixed self-assembled monolayers (SAMs) were prepared from binary solutions of 12-(2,2':6',2″-terpyridine-4'-yl)dodecane-1-thiol (TDT) and 1-decanethiol (DT). The SAMs and the order of the constituting molecules were analyzed by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and time-of-flight-secondary ion mass spectrometry (ToF-SIMS). The composition of the (TDT/DT)-SAMs and with it the surface density of terpyridyl groups correlates linearly with the relative concentrations of the two compounds in the solution used for depositing them. In marked contrast, the amount of terpyridine-coordinated Pd(II) ions significantly deviates from this trend with an optimum at a 1:3 ratio of TDT/DT. This indicates a major fraction of the terpyridines in TDT-rich SAMs not to be accessible for Pd(II) ion coordination. In agreement, NEXAFS spectroscopy reveals the alkyl backbones in TDT-rich SAMs not to be ordered, while they are preferentially upright oriented in the optimal 1:3-(TDT/DT)-SAMs. We interpret this in terms of terpyridine backfolding in TDT-rich SAMs, while they are located in accessible positions on top of the SAM in the 1:3-(TDT/DT)-SAM. While the alkyl backbones in the 1:3-(TDT/DT)-SAM are ordered, NEXAFS spectroscopy shows the terpyridyl groups not to have a preferential orientation in this SAM and thus retain enough flexibility to adjust to molecules that are deposited on top of the mixed SAM. In conclusion, the novel SAM does not undergo phase separation and consists predominantly of intermixed phases with adjustable surface density of quite flexible terpyridine anchor groups. The terpyridine-Pd(II) anchors are not only available for a future deposition of the next layer, but the metal ions also represent a sensitive probe for the accessibility of the terpyridyl groups. 相似文献
77.
Johannes Poppenberg Sebastian Richter Erik Darlatt Christoph H.-H. Traulsen Hyegeun Min Wolfgang E.S. Unger Christoph A. Schalley 《Surface science》2012,606(3-4):367-377
The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF3-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system. 相似文献
78.
79.
P. S. Unger 《Accreditation and quality assurance》2001,6(12):521-522
As of August 2001, 38 laboratory accreditation bodies of the International Laboratory Accreditation Cooperation (ILAC) have
signed the multi-lateral, mutual recognition arrangement (the ”ILAC Arrangement”) to promote the acceptance of accredited
test and calibration data. This Arrangement provides significant technical underpinning to international trade. Until now,
there has been no international mutual recognition agreement in laboratory accreditation, which has been a hindrance for some
types of international trade. The key to the Arrangement is the developing global network of accredited testing and calibration
laboratories that are assessed and recognised as being competent by ILAC Arrangement signatory accreditation bodies. The signatories
have, in turn, been peer-reviewed and shown to meet ILAC’s criteria for competence. Now that the ILAC Arrangement is in place,
governments can take advantage of it to further develop or enhance trade agreements. The ultimate aim is increased use and
acceptance by industry, as well as government, of the results from accredited laboratories, including results from laboratories
in other countries. In this way, the free-trade goal of ”a product tested once and accepted everywhere” can be realised. 相似文献
80.
B. Unger K. Rurack R. Müller U. Resch-Genger K. Buttke 《Journal of Sol-Gel Science and Technology》2000,19(1-3):799-802
Two fluorescent dyes were incorporated into sol-gel derived SiO2 matrices. The dye was added to SiO2 precursors of different degrees of pre-condensation and the spectroscopic properties of the immobilized dye were measured at various aging and drying stages of the resulting gels. The significant influence of the processing parameters on the spectroscopic properties is manifested in the relative intensity of a second red shifted emission band (550–560 nm), which was observed besides the typical coumarin emission band (495 nm). The appearance of this long wavelength emission might be attributed to dye aggregation or to other reactions with the ambient matrix forced by micro porosity phenomena. 相似文献