We explore the molecular properties of adsorbates that dramatically affect growth kinetics and morphology of the [100] face of archerite, also known as potassium dihydrogen phosphate (KH(2)PO(4) or KDP). Aqueous complexes of Al(III), Fe(III), and Cr(III) are known to affect KDP growth, albeit the actual step-pinning complex(es) is unknown. Using in situ atomic force microscopy (AFM), we measured changes in the growth rates of the [100] face of KDP with supersaturation in the presence of trace amounts of [Co(NH(3))(6)](3+), [Fe(CN)(6)](3-), eta(1)-[Co(NH(3))(5)HPO(4)](+), eta(2)-[Co(NH(3))(4)HPO(4)](+), eta(2)-[Co(NH(3))(4)P(2)O(7)H(2)](+), and [Rh(H(2)PO(4))(2)(H(2)O)(4)](+). Unlike in experiments using trivalent-metals, these complexes do not change stoichiometry or structure on the timescale of step motion, so that the actual molecular interactions that affect growth can be studied. Step velocity and morphology on the [100] face are unaffected by outer-sphere coordination complexes of either charge. Surprisingly, inner-sphere phosphatoammine complexes do not affect growth rates regardless of how the phosphate group is coordinated to the metal. However, doping the growth solution with [Rh(H(2)PO(4))(2)(H(2)O)(4)](+) results in profound step pinning, matching the behavior of KDP surfaces grown in the presence of Rh(III) after an equilibration period. Not only is an inner-sphere phosphate group needed to dock a trivalent metal to the step edge, but compatible hydrogen bonding of the remainder of the inner-sphere ligands with the bulk lattice is also essential. 相似文献
The combined influence of primary-level differences (L1-L2) and primary-frequency ratio (f2/f1) on distortion product otoacoustic emission (DPOAE) level was investigated in 20 normal-hearing subjects. DPOAEs were recorded with continuously varying stimulus levels [Neely et al. J. Acoust. Soc. Am. 117, 1248-1259 (2005)] for the following stimulus conditions: f2= 1, 2, 4, and 8 kHz and f2/f1=1.05 to 1.4; various L1-L2, including one individually optimized to produce the largest DPOAE. For broadly spaced primary frequencies at low L2 levels, the largest DPOAEs were recorded when L1 was much higher than L2, with L1 remaining relatively constant as L2 increased. As f2/fl decreased, the largest DPOAEs were observed when L1 was closer to L2 and increased as L2 increased. Optimal values for L1-L2 and f2 f1 were derived from these data. In general, average DPOAE levels for the new L1-L2 and f2/f1 were equivalent to or larger than those observed for other stimulus combinations, including the L1-L2 described by Kummer et al. [J. Acoust. Soc. Am. 103, 3431-3444 (1998)] and those defined by Neely et al. in which L1-L2 was evaluated, but f2/f1 was fixed at 1.2. 相似文献
A new model for the location and distribution of carbonate ions in carbonated apatite was used to assign the IR spectra of A- and AB-carbonated apatites. The percentage of total carbonate as measured by the mass loss in the TGA of these compounds is in good agreement with the percentage obtained by combustion analysis. The decomposition of pure A-type carbonate appears at temperatures of 985–1123 °C, whereas the decomposition of AB-type carbonated apatites occurs in the range of 600–800 °C. This difference is attributed to changes in the environment of channel carbonate brought about by B-type substitution of carbonate for phosphate. In the presence of sodium ions, the channel is changed by substitution of sodium for calcium in order to accommodate the difference between the charge of the carbonate and phosphate ions. A thermodynamic cycle is introduced to rationalize the differences in decomposition temperatures of A- and B-type carbonate. Preferential loss of B-type carbonate upon heating to 600 °C also suggests the migration of B-type carbonate to A-sites.
The continued rise in the extraction of unconventional oil and gas across the globe poses many questions about how to manage these relatively new waste‐streams. Produced water, the primary waste by‐product, contains a diverse number of anthropogenic additives together with the numerous hydrocarbons extracted from the well. Due to potential environmental hazards, it is critical to characterize the chemical composition of this type of waste before proper disposal or remediation/reuse. In this work, a thin film solid phase microextraction approach was developed and optimized to characterize produced water. The thin film device consisted of hydrophilic‐lipophilic balance particles embedded in polydimethylsiloxane and immobilized on a carbon mesh surface. These devices were chosen to provide broad extraction coverage and high reusability. Various parameters were evaluated to ensure reproducible results while minimizing analyte loss. This optimized protocol, consisting of a 15 min extraction followed by a short (3 s) rinsing step, enabled the reproducible analysis of produced water without any sample pretreatment. Extraction efficiency was suitable for both produced water additives and hydrocarbons. The developed approach was able to tentatively identify a total of 201 compounds from produced water samples, by using one‐dimensional gas chromatography hyphenated to mass spectrometry and data deconvolution. 相似文献
A new efficient photocaging system with a fluorescence reporting function has been developed. The photolabile latch is based on adducts of C-nucleophiles with aromatic ketones, such as thioxanthones and xanthones. The system is designed to quantify the release of biological effectors and to monitor their spatial distribution and localization by single- and two-photon fluorescence microscopy. In the armed state the ketone's conjugation is disrupted by nucleophilic addition, resulting in a blue shift of the absorption maxima and a dramatic decrease in fluorescence intensity. The mechanism of the photoinduced uncaging involves homolytic C-C bond fragmentation followed by radical disproportionation, regenerating the carbonyl moiety and restoring fluorescence. The uncaging can be initiated via either a one- or two-photon process, offering a new powerful tool for molecular life sciences. The synthesis and uncaging of dendrimer- and polymeric bead-based model systems are described. 相似文献
The E-4,4'-bis[di(p-anisyl)amino]stilbene cation is a class-III mixed-valence species with electronic coupling comparable to that in its biphenyl-bridged analogue, whereas its tolane-bridged analogue belongs to class II. 相似文献
Reversible ethylene fixation in lanthanide chemistry is demonstrated by the SmII derivatives [R8-calix-pyrrole)(Et2O)Sm{Li(thf)2}{Li(μ3-OCH=CH2)}] (R=Et, {−(CH2)5−}0.5), which react with ethylene to afford the corresponding dinuclear complexes (see picture). 相似文献