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101.
Lothar Helm Karen Deutsch Edward A. Deutsch Andr E. Merbach 《Helvetica chimica acta》1992,75(1):210-217
The kinetics of pyridine exchange on trans-[MO2(py)4]+ have been followed by 1H-NMR in CD3NO2 for M = Re, Tc: k298S?1 = (5.5 ± 0.1) × 10?6, 0.04 ± 0.02; ΔH≠/kJmol?1 = 111 ± 3, 101 ± 9; ΔS≠/JK?1mol?1 = +28 ± 10, +68 ± 35. For the Rev complex, pyridine and oxygen exchanges have been measured simultaneously by 1H- and 17O-NMR in deuterated water: k298/s?1 = (8.6 ± 0.2) × 10?6 (py), (14.5 ± 0.3) × 10?6 (oxygen); ΔH≠/kJmol?1 = 111 ± 1, 91 ± 1; ΔS /JK?1mol?1 = +32 ± 3, ?32 ± 4. For both complexes, the rate law for pyridine exchange is first-order in complex and zero-order in pyridine; together with the activation parameter values, and the fact that the rate does not depend significantly on the nature of the solvent, this strongly implies the operation of a dissociative mechanism. The ratio of pyridine exchange rates for the Tc and Re complexes at room temperature is ca. 8000. The consequences of these observations for radiopharmaceutical synthesis are discussed. 相似文献
102.
New five-coordinate Pt(IV) complexes [{(o-R2-p-R'-C6H2)NC(R' ')}2CH]PtMe3 (R, R', R' ' = alkyl or H) are reported. The complex with R = Me, R' = tBu, R' ' = Me generates unsaturated Pt(II) species capable of alkane C-H bond activation and stoichiometric dehydrogenation. 相似文献
103.
3-Diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II) — Synthesis and Structure Bis-(N′, N′-diethyl-N-benzoylselenoureato)nickel(II) reacts with diphosgene in benzene to 3-diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II). Its structure is confirmed by RKSA and ESCA. The compound consists of cations, which are planar fivemembered rings and of tetrahedral tetrachloroniccolate(II) anions. The complex is isomorphic with 3-diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate(II). 相似文献
104.
Enhanced fluorescence from arrays of nanoholes in a gold film 总被引:1,自引:0,他引:1
Brolo AG Kwok SC Moffitt MG Gordon R Riordon J Kavanagh KL 《Journal of the American Chemical Society》2005,127(42):14936-14941
Arrays of sub-wavelength holes (nanoholes) in gold films were used as a substrate for enhanced fluorescence spectroscopy. Seven arrays of nanoholes with distinct periodicities (distances between the holes) were fabricated. The arrays were then spin-coated with polystyrene films containing different concentrations of the fluorescent dye oxazine 720. The dye was excited via resonant extraordinary transmission of the laser source through the nanoholes. Enhanced fluorescence was observed when the geometric characteristics of the arrays allowed for an enhancement in the transmitted excitation. This enhancement occurred via surface plasmon excitation by the laser and a consequential increase in the local electromagnetic field in a sub-wavelength region at the metal-film interface. It was demonstrated that the sensitivity of the fluorescence measurement (change in signal vs change in dye concentration in the polymer film) is significantly larger at the surface plasmon resonance conditions than that obtained from equivalent films on glass substrates. Enhancement factors for the fluorescence emission were calculated for each array, with a maximum enhancement of close to 2 orders of magnitude as compared to the emission of films on glass. The results presented here indicate that arrays of nanoholes are interesting substrates for the development of fluorescence sensors based on surface plasmon resonance, as they provide a platform that allows both spatial confinement and enhancement of excitation light. Moreover, the collinear characteristics of the present optical setup, due to the resonant extraordinary transmission through the nanohole arrays, are more conducive to miniaturization and chip integration than more traditional experimental geometries. 相似文献
105.
The Compressibility of pH‐Sensitive Microgels at the Oil–Water Interface: Higher Charge Leads to Less Repulsion 下载免费PDF全文
Dipl.‐Chem. Karen Geisel Prof. Dr. Lucio Isa Prof. Dr. Walter Richtering 《Angewandte Chemie (International ed. in English)》2014,53(19):4905-4909
pH‐responsive microgels are unique stabilizers for stimuli‐sensitive emulsions that can be broken on demand by changing the pH value. However, recent experiments have indicated that electrostatic interactions play a different role to that in conventional Pickering emulsions. The influence of charges on the interactions between microgels at the oil–water interface is now described. Compression isotherms of microgels with different charge density and architecture were determined in a Langmuir trough, and counter‐intuitive results were obtained: Charged microgels can be compressed more easily than uncharged microgels. The compressibility of microgels is thus not determined by direct Coulomb repulsion. Instead, the different swelling of the microgels in the charged and the uncharged states is proposed to be the key parameter. 相似文献
106.
Sharpless KE Lindstrom RM Nelson BC Phinney KW Rimmer CA Sander LC Schantz MM Spatz RO Thomas JB Turk GC Wise SA Wood LJ Yen JH 《Journal of AOAC International》2010,93(4):1262-1274
Standard Reference Material (SRM) 1849 Infant/Adult Nutritional Formula has been issued by the National Institute of Standards and Technology (NIST) as a replacement for SRM 1846 Infant Formula, issued in 1996. Extraction characteristics of SRM 1846 have changed over time, as have NIST's analytical capabilities. While certified mass fraction values were provided for five constituents in SRM 1846 (four vitamins plus iodine), certified mass fraction values for 43 constituents are provided in SRM 1849 (fatty acids, elements, and vitamins) and reference mass fraction values are provided for an additional 43 constituents including amino acids and nucleotides, making it the most extensively characterized food-matrix SRM available from NIST. 相似文献
107.
Karen A. Wulfeck-Kleier Michael D. Ybarra Thomas F. Speth Matthew L. Magnuson 《Journal of chromatography. A》2010,1217(5):676-682
Although the herbicide atrazine has been reported to not react measurably with free chlorine during drinking water treatment, this work demonstrates that at contact times consistent with drinking water distribution system residence times, a transformation of atrazine can be observed. Some transformation products detected through the use of high performance liquid chromatography–electrospray mass spectrometry are consistent with the formation of N-chloro atrazine. The effects of applied chlorine, pH, and reaction time on the transformation reaction were studied to help understand the practical implications of the transformation on the accurate determination of atrazine in drinking waters. The errors in the determination of atrazine are a function of the type of dechlorinating agent applied during sample preparation and the analytical instrumentation utilized. When a reductive dechlorinating agent, such as sodium sulfite or ascorbic acid is used, the quantification of the atrazine can be inaccurate, ranging from 2-fold at pH 7.5 to 30-fold at pH 6.0. The results suggest HPLC/UV and ammonium chloride quenching may be best for accurate quantification. Hence, the results also appear to have implications for both compliance monitoring and health effects studies that utilize gas chromatography analysis with sodium sulfite or ascorbic acid as the quenching agent. 相似文献
108.
The processes of lactic acid production include two key stages, which are (a) fermentation and (b) product recovery. In this
study, free cell of Bifidobacterium longum was used to produce lactic acid from cheese whey. The produced lactic acid was then separated and purified from the fermentation
broth using combination of nanofiltration and reverse osmosis membranes. Nanofiltration membrane with a molecular weight cutoff
of 100–400 Da was used to separate lactic acid from lactose and cells in the cheese whey fermentation broth in the first step.
The obtained permeate from the above nanofiltration is mainly composed of lactic acid and water, which was then concentrated
with a reverse osmosis membrane in the second step. Among the tested nanofiltration membranes, HL membrane from GE Osmonics
has the highest lactose retention (97 ± 1%). In the reverse osmosis process, the ADF membrane could retain 100% of lactic
acid to obtain permeate with water only. The effect of membrane and pressure on permeate flux and retention of lactose/lactic
acid was also reported in this paper. 相似文献
109.
L. Renee Ruhaak Sandra L. Taylor Suzanne Miyamoto Karen Kelly Gary S. Leiserowitz David Gandara Carlito B. Lebrilla Kyoungmi Kim 《Analytical and bioanalytical chemistry》2013,405(14):4953-4958
Many studies focused on the discovery of novel biomarkers for the diagnosis and treatment of disease states are facilitated by mass spectrometry-based technology. HPLC coupled to mass spectrometry is widely used; miniaturization of this technique using nano-liquid chromatography (LC)-mass spectrometry (MS) usually results in better sensitivity, but is associated with limited repeatability. The recent introduction of chip-based technology has significantly improved the stability of nano-LC-MS, but no substantial studies to verify this have been performed. To evaluate the temporal repeatability of chip-based nano-LC-MS analyses, N-glycans released from a serum sample were repeatedly analyzed using nLC-PGC-chip-TOF-MS on three non-consecutive days. With an average inter-day coefficient of variation of 4 %, determined on log10-transformed integrals, the repeatability of the system is very high. Overall, chip-based nano-LC-MS appears to be a highly stable technology, which is suitable for the profiling of large numbers of clinical samples for biomarker discovery. 相似文献
110.
Laurens van Gelderen Gadi Rothenberg V. Roberto Calderone Karen Wilson N. Raveendran Shiju 《应用有机金属化学》2013,27(1):23-27
Copper immobilized on a functionalized silica support is a good catalyst for the homocoupling of terminal alkynes. The so‐called Glaser–Hay coupling reaction can be run in air with catalytic amounts of base. The copper catalyst is active for multiple substituted alkynes, in both polar and non‐polar solvents, with good to excellent yields (75–95%). Depending on the alkyne, full conversion can be achieved within 3–24 h. The catalyst was characterized by TGA, inductively coupled plasma and X‐ray photoelectron spectroscopy. Leaching tests confirm that the catalyst is and remains heterogeneous. Importantly, the overall reaction requires only alkyne and oxygen (in this case, air) as reagents, making this a clean catalytic oxidative coupling reaction. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献