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61.
62.
Chantry RL Siriwatcharapiboon W Horswell SL Logsdail AJ Johnston RL Li ZY 《The journal of physical chemistry. C, Nanomaterials and interfaces》2012,116(18):10312-10317
This study focuses on the deposition and growth mode of rhodium (Rh) on gold (Au) seed nanorods (NRs). Using a combination of scanning transmission electron microscopy imaging, energy-dispersive X-ray spectroscopy, and UV-visible absorption spectroscopy, we show that Rh deposition results in an uneven overlayer morphology on the Au NR seeds, with a tendency for Rh deposition to occur preferentially on the Au NR ends. The results suggest that complex and kinetically driven metal-metal interactions take place in this system. 相似文献
63.
Aurica Farcas Giulia Tregnago Ana‐Maria Resmerita Sarah Taleb Dehkordi Sophie Cantin Fabrice Goubard Pierre‐Henri Aubert Franco Cacialli 《Journal of polymer science. Part A, Polymer chemistry》2014,52(4):460-471
The photophysical properties of two polyrotaxanes ( PFBTh?PSβCD and PFBTh?PMeβCD ) composed of fluorene and bithiophene encapsulated into permodified β‐cyclodextrin cavities have been investigated and compared with those of the reference PFBTh . Rotaxane formation results in improvements of the thermal stability, solubility in common organic solvents, as well as better film forming ability combined with a high transparency. As expected PFBTh and its encapsulated forms absorb at wavelengths beyond 510 nm, and time‐resolved photoluminescence (PL) in solution shows a well‐define vibronic structures with a predominance of the 0‐0 transitions and an energy difference of 0.16 eV. The fluorescence lifetimes follow a monoexponential decay with a value τ = 630 ± 30 ps. Atomic force microscopy, AFM, indicated a tendency of polyrotaxanes to organize into fibers. The advancing contact angles indicated higher surface hydrophobicity and lower surface free‐energy values for polyrotaxanes compared with their unthreaded analogues. The device based on PFBTh?PSβCD: PCBM in a 1/1 w/w ratio under simulated AM 1.5G illumination at 100 mW cm?2 exhibited improved photovoltaic parameters of cells, resulted in high Voc (0.68 V), Jsc (1.65 mA cm?2), FF (31.6%), and PCE (0.35) values, compared with PFBTh or PFBTh?PMeβCD , respectively. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 460–471 相似文献
64.
65.
Nassim N. Taleb 《Physica A》2010,389(17):3503-3507
This paper establishes the case for a fallacy of economies of scale in large aggregate institutions and the effects of scale risks. The problem of rogue trading and excessive risk taking is taken as a case example. Assuming (conservatively) that a firm exposure and losses are limited to its capital while external losses are unbounded, we establish a condition for a firm not to be allowed to be too big to fail. In such a case, the expected external losses second derivative with respect to the firm capital at risk is positive. Examples and analytical results are obtained based on simplifying assumptions and focusing exclusively on the risk externalities that firms too big to fail can have. 相似文献
66.
67.
Lewis Couchman Sarah L. Belsey Simon A. Handley Robert J. Flanagan 《Analytical and bioanalytical chemistry》2013,405(29):9455-9466
Therapeutic drug monitoring (TDM) requires timely results in order to be clinically helpful. Such assays, when carried out using mass spectrometry-based methods, typically involve a batched sample approach with multipoint calibration. Isotopic internal calibration offers the possibility of open-access mass spectrometric analysis with consequent shortening of turnaround times. We measured plasma clozapine and N-desmethylclozapine (norclozapine) concentrations in (1) external quality assessment (EQA) samples (N?=?22) and (2) patient samples (N?=?100) using liquid chromatography-tandem mass spectrometry with isotopic internal calibration (ICAL-LC-MS/MS). Analyte concentrations were calculated from graphs of the response of three internal calibrators (clozapine-D4, norclozapine-D8, and clozapine-D8) against concentration. Precision (% RSD) and accuracy (% nominal concentrations) for the ICAL-LC-MS/MS method were <5 % and 104–112 %, respectively for both analytes. There was excellent agreement with consensus mean and with ‘spiked’ values on analysis of the EQA samples (R 2?=?0.98 and 0.97, respectively, inclusive of clozapine and norclozapine results). In the patient samples, comparison against traditionally calibrated HPLC-UV and LC-MS/MS methods showed excellent agreement (R 2?=?0.97 or better) with small albeit significant mean differences (<0.041 and <0.042 mg/L for clozapine and norclozapine, respectively). These differences probably reflect discrepancies in the in-house preparation of calibrators and/or interference in the UV method. Internal calibration offers a novel and attractive alternative to traditionally calibrated batch analysis in analytical toxicology. The method described has been validated for use in the high-throughput TDM of clozapine and norclozapine, and allows for (1) same-day reporting of results and (2) significant cost savings. Figure
A typical internal calibration curve produced using three different isotopically-labelled analogues of clozapine and norclozapine (clozapine-D4, norclozapine-D8 and clozapine-D8) and interpolation of the clozapine and norclozapine concentrations from an extracted patient sample (calculated clozapine and norclozapine 0.47 and 0.31 mg/L, respectively) 相似文献
68.
Sarah J. R. Staton Josemar A. Castillo Thomas J. Taylor Pierre Herckes Mark A. Hayes 《Analytical and bioanalytical chemistry》2013,405(1):351-357
A substantial portion of the atmospheric particle budget is of biological origin (human and animal dander, plant and insect debris, etc.). These bioaerosols can be considered information-rich packets of biochemical data specific to the organism of origin. In this study, bioaerosol samples from various indoor environments were analyzed to create identifiable patterns attributable to a source level of occupation. Air samples were collected from environments representative of human high-traffic- and low-traffic indoor spaces along with direct human skin sampling. In all settings, total suspended particulate matter was collected and the total aerosol protein concentration ranged from 0.03 to 1.2 μg/m3. High performance liquid chromatography was chosen as a standard analysis technique for the examination of aqueous aerosol extracts to distinguish signatures of occupation compared to environmental background. The results of this study suggest that bioaerosol “fingerprinting” is possible with the two test environments being distinguishable at a 97 % confidence interval. Figure
Generalized schematic of human debris-based occupation detection. The various human occupation-related aerosolized material are collected via the filtration assembly along with other non-related aerosolized material. The collected material was then analyzed for total protein concentration as well as coarsely separated to generated unique pattern profiles. These profiles are information-rich enough to identify human occupation in an indoor space 相似文献
69.
Sarah A. Hackenmueller 《合成通讯》2013,43(10):1439-1446
Thyroid hormones undergo extensive metabolism to regulate hormone activity. A labeled thyroid hormone would be useful to track hormone metabolism through various pathways. While radiolabeled thyroid hormones have been synthesized and used for in vivo studies, a stable isotope labeled form of thyroid hormone is required for studying thyroid hormone metabolism by LC-MS/MS, an analytical technique that has certain advantages without the complications of radioactivity. Here we report the synthesis of 13C9-15N-T2 and 13C9-15N-T4, two labeled thyroid hormone derivatives suitable for in vivo LC-MS/MS studies. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
70.
Daniel R. Zuidema Sarah L. Williams Katherine J. Wert Karin J. Bosma Abigail L. Smith Robert C. Mebane 《合成通讯》2013,43(19):2927-2931
Aryl ketones are readily deoxygenated to their corresponding aryl alkanes upon treatment with Raney nickel catalyst in boiling 2-propanol.