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991.
A detailed analysis of the origins of vibrational frequency shifts of diatomic molecules (I2 and ICl) in a rare gas (Xe) liquid is presented. Specifically, vibrationally adiabatic mixed quantum-classical molecular dynamics simulations are used to obtain the instantaneous frequency shifts and correlate the shifts to solvent configurations. With this approach, important mechanistic questions are addressed, including the following: How many solvent atoms determine the frequency shift? What solvent atom configurations lead to blue shifts, and which lead to red shifts? What is the effect of solute asymmetry? The mechanistic analysis can be generally applied and should be useful in understanding what information is provided by infrared and Raman spectra about the environment of the probed vibrational mode. 相似文献
992.
Díaz RI Regourd J Santacroce PV Davis JT Jakeman DL Thompson A 《Chemical communications (Cambridge, England)》2007,(26):2701-2703
A new class of prodigiosenes with stability-enhancing functionalities appended to the C-ring were found to transport chloride anions through liposomal membranes, as well as to induce copper-mediated DNA cleavage. 相似文献
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995.
Most modern cochlear-implant speech processors convey speech-envelope information using amplitude-modulated pulse trains. The use of higher-rate carrier pulse trains allows more envelope detail in the signal. However, neural response properties could limit the efficacy of high-rate carriers. This study examined effects of carrier rate and stimulation site, on psychophysical modulation detection thresholds (MDTs). Both of these variables could affect the neural representation of the carrier and thus affect perception of the modulation. Twelve human subjects with cochlear implants were tested. Phase duration of symmetric biphasic pulses was modulated sinusoidally at 40 Hz. MDTs were determined for monopolar stimulation at two carrier rates [250 and 4000 pulses/s (pps)], three stimulation sites (basal, middle, and apical), and five stimulus levels (10%, 30%, 50%, 70%, and 90% of the dynamic range). MDTs were lower for 250 pps carriers than for 4000 pps carriers in 71% of the 180 cases studied. Effects of carrier rate were greatest at the apical stimulation site and effects of stimulation site on MDTs depended on carrier rate. The data suggest a distinct disadvantage to using carrier pulse rates as high as 4000 pps. Stimulation site should be considered in evaluating modulation detection ability. 相似文献
996.
Novel use of glow discharge optical emission spectroscopy (GDOES) to study corrosion of AA2024‐T3 in the presence and absence of inhibitors 下载免费PDF全文
Recent interest in environmentally friendly alternatives to chromate‐based corrosion inhibitors has led to the development of a range of novel coating formulations. The work described herein is aimed at developing a novel methodology to contribute to investigation of the self‐healing and active corrosion protection of the new coatings. An experimental procedure has been developed to model a defect in the coating by fixing coated specimens in close proximity to the uncoated AA2024‐T3, each separated by a narrow gap containing sodium chloride solution. After exposure to the corrosive environment, elemental depth profiles of the uncoated specimens were acquired by glow discharge optical emission spectroscopy (GDOES). The depth profiles of selected elements (notably aluminium, oxygen and copper) were shown to have characteristics which can be correlated with bulk surface roughening/intensity of corrosion, the thickness of the corroded layer and de‐alloying/re‐distribution of copper. An unanticipated inhibitory effect was noted in the case of a coating doped with γ‐Al2O3 (γ‐alumina or AluOx). Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
997.
Effectiveness of 2‐mercaptobenzothiazole, 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors on AA 2024‐T3 assessed by electrochemical methods 下载免费PDF全文
Andronikos C. Balaskas Michele Curioni George E. Thompson 《Surface and interface analysis : SIA》2015,47(11):1029-1039
In this study, the effectiveness of 2‐mercaptobenzothiazole (2‐MBT), 8‐hydroxyquinoline and benzotriazole as corrosion inhibitors for AA 2024‐T3 aluminium alloy was evaluated. The corrosion behaviour in the presence of each compound was investigated by image‐assisted electrochemical noise analysis, electrochemical impedance spectroscopy, potentiodynamic polarization and the split cell technique. It was found that 2‐MBT has superior inhibition properties compared with the other inhibitors. In particular, the specimens immersed in 3.5% NaCl in the presence of 2‐MBT displayed high values of noise resistance that were maintained for over 400 h of testing, and high values of low‐frequency impedance, measured after immersion for 24 h. The split cell technique and potentiodynamic polarization tests indicated that only 2‐MBT decreases significantly both the anodic and the cathodic reaction rates. Scanning electron microscopy observations and energy dispersive X‐ray measurements complement the findings from electrochemical measurements indicating that only 2‐MBT protects the second phase particles, preventing dealloying, trenching and initiation of corrosion. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd. 相似文献
998.
2‐Aminoethanol Extraction as a Method for Purifying Sc3N@C80 and for Differentiating Classes of Endohedral Fullerenes on the Basis of Reactivity 下载免费PDF全文
Evan A. Sarina Dr. Brandon Q. Mercado Dr. Jimmy U. Franco Dr. Christopher J. Thompson Dr. Michael L. Easterling Prof. Dr. Marilyn M. Olmstead Prof. Dr. Alan L. Balch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(47):17035-17043
Extraction with 2‐aminoethanol is an inexpensive method for removing empty cage fullerenes from the soluble extract from electric‐arc‐generated fullerene soot that contains endohedral metallofullerenes of the type Sc3N@C2n (n=34, 39, 40). Our method of separation exploits the fact that C60, C70, and other larger, empty cage fullerenes are more susceptible to nucleophilic attack than endohedral fullerenes and that these adducts can be readily extracted into 2‐aminoethanol. This methodology has also been employed to examine the reactivity of the mixture of soluble endohedral fullerenes that result from doping graphite rods used in the Krätschmer–Huffman electric‐arc generator with the oxides of Y, Lu, Dy, Tb, and Gd. For example, with Y2O3, we were able to detect by mass spectrometry several new families of endohedral fullerenes, namely Y3C108 to Y3C126, Y3C107 to Y3C125, Y4C128 to Y4C146, that resisted reactivity with 2‐aminoethanol more than the empty cage fullerenes and the mono‐ and dimetallo fullerenes. The discovery of the family Y3C107 to Y3C125 with odd numbers of carbon atoms is remarkable, since fullerene cages must involve even numbers of carbon atoms. The newly discovered families of endohedral fullerenes with the composition M4C2n (M=Y, Lu, Dy, Tb, and Gd) are unusually resistant to reaction with 2‐aminoethanol. Additionally, the individual endohedrals, Y3C112 and M3C102 (M=Lu, Dy, Tb and Gd), were remarkably less reactive toward 2‐aminoethanol. 相似文献
999.
Dr. Hao Sun Dr. Wei Cao Dr. Nanzhi Zang Dr. Tristan D. Clemons Georg M. Scheutz Ziying Hu Dr. Matthew P. Thompson Yifei Liang Maria Vratsanos Xuhao Zhou Wonmin Choi Prof. Dr. Brent S. Sumerlin Prof. Dr. Samuel I. Stupp Prof. Dr. Nathan C. Gianneschi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19298-19304
Herein, we report the photoinitiated polymerization-induced self-assembly (photo-PISA) of spherical micelles consisting of proapoptotic peptide–polymer amphiphiles. The one-pot synthetic approach yielded micellar nanoparticles at high concentrations and at scale (150 mg mL−1) with tunable peptide loadings up to 48 wt. %. The size of the micellar nanoparticles was tuned by varying the lengths of hydrophobic and hydrophilic building blocks. Critically, the peptide-functionalized nanoparticles imbued the proapoptotic “KLA” peptides (amino acid sequence: KLAKLAKKLAKLAK) with two key properties otherwise not inherent to the sequence: 1) proteolytic resistance compared to the oligopeptide alone; 2) significantly enhanced cell uptake by multivalent display of KLA peptide brushes. The result was demonstrated improved apoptosis efficiency in HeLa cells. These results highlight the potential of photo-PISA in the large-scale synthesis of functional, proteolytically resistant peptide–polymer conjugates for intracellular delivery. 相似文献
1000.
Magnetization and neutron diffraction studies of the 2D S = 1/2 antiferromagnet, K2V3O8, indicate an ordered state exhibiting weak ferromagnetism and field-induced spin reorientations. Of particular interest is the behavior in a basal plane magnetic field where a unique spin reorientation is observed in which the spins rotate from the easy c axis to the basal plane while remaining normal to the applied field. The experimental observations are well described by a two spin exchange model incorporating Heisenberg and Dzyaloshinskii-Moriya interactions with an additional c-axis anisotropy. 相似文献