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81.
Results and new theory are presented for the uncoated and coated facet reflectivity of a shallowly buried waveguide, taking account of the diffracting corner present at the air–semiconductor interface. The corner effects are shown to be most significant in the case of coated facets. The analysis also predicts the asymmetry introduced into the radiation pattern.  相似文献   
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The present paper provides a detailed analysis of the analyte-wall adsorption effects in nanochannels, including a random walk study of the analyte-wall collision frequency, and uses these insights to estimate wall desorption times from chromatographic experiments in nanochannels. Using coumarin dye analytes and using a methanol/water mixture buffered at pH 3 in 120-nm deep channels, the surface desorption times on naked fused-silica glass were found to be maximally of the order of 60 to 150 μs, while they were found to be on the order of 100 to 500 μs on a hydrophobically coated wall. These nonzero adsorption and desorption times lead to an additional band broadening when conducting chromatographic separations. Shear-driven flows, requiring a noncoated moving wall and a stationary coated wall, intrinsically turn out to be more prone to this effect than pressure-driven or electro-driven flows for example. The present study also shows that, interestingly, the number of analyte-wall collisions increases with the inverse of the channel depth and not with its second power, as would be expected from the Einstein–Smoluchowski relationship for molecular diffusion.  相似文献   
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Zusammenfassung Mikrogramm-Mengen von Arsen(III) können nach Ausschütteln mit Benzol aus salzsauren Lösungen mit der differentiellen Pulse-Polarographie bestimmt werden. Die polarographische Bestimmung kann entweder direkt im organischen Extrakt nach Zusatz einer nichtwäßrigen Grundlösung oder nach Verdampfen der organischen Phase über einer wäßrigen Grundlösung durchgeführt werden. Die Bedingungen für die Reduktion des Arsens(V) in schwefelsauren Aufschlußlösungen zum anschließenden Ausschütteln und für die polarographische Bestimmung werden angegeben.
Differential-pulse-polarographic determination of arsenic after extraction of arsenic(III) chloride
Summary After extraction with benzene from hydrochloric acid solutions microgram amounts of arsenic(III) can be determined by differential-pulse-polarography. The polarographic determination can be performed either in the organic extract after addition of a non-aqueous supporting electrolyte or after evaporation of the organic solvent over a suitable aqueous electrolyte. Conditions for the reduction of arsenic (V) in sulfuric acid decomposition solutions prior to extraction and further polarographic determination are dealt with.


Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbandes der Chemie-Fonds der Chemie unterstützt.  相似文献   
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Rapid determination of gross alpha and beta emitters in urine by liquid scintillation counting is discussed. This method is based on direct addition of urine into scintillation cocktail. 241Am, 239Pu and 90Sr were selected as model radionuclides. The LSA Hidex 300 SL equipped with Triple-Double-Coincidence-Ratio technique was used for sample measurement. The work focused on optimizing the LSC cocktail to urine volume ratio with respect to the model radionuclides. The overall efficiencies for 241Am, 239Pu and 90Sr were greater than 92 %; therefore, this method would be suitable for rapid determination of gross alpha/beta activity.  相似文献   
88.
Interaction between similarly charged surfaces can be attractive at high electrostatic coupling constants Ξ = l(B)Z(2)/μ(GC), where l(B) is the Bjerrum length, μ(GC) the Gouy-Chapman length, and Z the valency of counterions. While this effect has been studied previously in detail, as a function of surface charge density and valency of the pointlike counterions, much less is known about the effect of counterion size. We apply the Wang-Landau sampling Monte Carlo (MC) simulation method to compute the free energy F as a function of the scaled distance between the plates D?=D/μ(GC) for a range of Ξ and scaled counterion radii R?=R/μ(GC). We find that for large Ξ and small ion radius, there is a global equilibrium distance D?=D?(eq)=2(1+R?), correctly giving the expected value at the point counterion limit. With increasing R? the global minimum in F(D?) changes to a metastable state and finally this minimum vanishes when R? reaches a critical value, which depends on Ξ. We present a state diagram indicating approximate boundaries between these three regimes. The Wang-Landau MC method, as it is applied here, offers a possibility to study a wide spectrum of extended problems, which cannot be treated by the use of contact value theorem.  相似文献   
89.
Herein we describe the design and synthesis of the first series of di‐functional ligands for the directed construction of inorganic‐protein frameworks. The synthesized ligands are composed of a metal‐ion binding moiety (terpyridine‐based) conjugated to an epoxysuccinyl peptide, known to covalently bind active cysteine proteases through the active‐site cysteine. We explore and optimize two different conjugation chemistries between the di‐functionalized metal‐ion ligand and the epoxysuccinyl‐containing peptide moiety: peptide‐bond formation (with limited success) and CuI‐catalysed click chemistry (with good results). Further, the complexation of the synthesized ligands with FeII and NiII ions is investigated: the di‐functional ligands are confirmed to behave similarly to the parent terpyridine. As designed, the peptidic moiety does not interfere with the complexation reaction, in spite of the presence of two triazole rings that result from the click reaction. ES‐MS together with NMR and UV/Vis studies establish the structure, the stoichiometry of the complexation reactions, as well as the conditions under which chemically sensitive peptide‐containing polypyridine ligands can undergo the self‐assembly process. These results establish the versatility of our approach and open the way to the synthesis of di‐functional ligands containing more elaborated polypyridine ligands as well as affinity labels for different enzyme families. As such, this paper is the first step towards the construction of robust supramolecular species that cover a size‐regime and organization level previously unexplored.  相似文献   
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