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961.
Simultaneous Detection of Single Attoliter Droplet Collisions by Electrochemical and Electrogenerated Chemiluminescent Responses 下载免费PDF全文
Jeffrey E. Dick Dr. Christophe Renault Dr. Byung‐Kwon Kim Prof. Dr. Allen J. Bard 《Angewandte Chemie (International ed. in English)》2014,53(44):11859-11862
We provide evidence of single attoliter oil droplet collisions at the surface of an ultra‐microelectrode (UME) by the observation of simultaneous electrochemical current transients (i–t curves) and electrogenerated chemiluminescent (ECL) transients in an oil/water emulsion. An emulsion system based on droplets of toluene and tri‐n‐propylamine (2:1 v/v) emulsified with an ionic liquid and suspended in an aqueous continuous phase was formed by ultrasonification. When an ECL luminophore, such as rubrene, is added to the emulsion droplet, stochastic events can be tracked by observing both the current blips from oxidation at the electrode surface and the ECL blips from the follow‐up ECL reaction, which produces light. This report provides a means of studying fundamental aspects of electrochemistry using the attoliter oil droplet and offers complementary analytical techniques for analyzing discrete collision events, size distribution of emulsion systems, and individual droplet electroactivity. 相似文献
962.
963.
Lihong Liu Prof. Bin He Dr. Qian Liu Dr. Zhaojun Yun Xueting Yan Dr. Yanmin Long Prof. Guibin Jiang 《Angewandte Chemie (International ed. in English)》2014,53(52):14476-14479
We have developed a new method for the identification and accurate size characterization of nanoparticles (NPs) in complex media based on capillary electrokinetic (CE) separation coupled to inductively coupled plasma mass spectrometry (ICP‐MS). Through mass scanning and Gaussian fitting of electropherogram peaks, we can obtain multidimensional information on chemical compositions, size distributions, and ionic species of multiple NPs in a single run. The results are more accurate than those obtained by using conventional methods. This method provides a powerful tool for investigating polydisperse NP systems and rapid screening of NP‐containing products. 相似文献
964.
Dr. Matthias Daxner Prof. Stephan Denifl Prof. Paul Scheier Prof. Andrew M. Ellis 《Angewandte Chemie (International ed. in English)》2014,53(49):13528-13531
The self‐assembly of salt nanocrystals from chemical reactions inside liquid helium is reported for the first time. Reaction is initiated by an electron impacting a helium nanodroplet containing sodium atoms and SF6 molecules, leading to preferential production of energetically favorable structures based on the unit cell of crystalline NaF. These favorable structures are observed as magic number ions (anomalously intense peaks) in mass spectra and are seen in both cationic and anionic channels in mass spectra, for example, (NaF)nNa+ and (NaF)nF?. In the case of anions the self‐assembly is not directly initiated by electrons: the dominant process involves resonant electron‐induced production of metastable electronically excited He? anions, which then initiate anionic chemistry by electron transfer. 相似文献
965.
Dynamic and Quantitative Control of the DNA‐Mediated Growth of Gold Plasmonic Nanostructures 下载免费PDF全文
Dr. Jianlei Shen Lifeng Xu Dr. Chunpeng Wang Dr. Hao Pei Prof.Dr. Renzhong Tai Prof.Dr. Shiping Song Prof.Dr. Qing Huang Prof.Dr. Chunhai Fan Prof.Dr. Gang Chen 《Angewandte Chemie (International ed. in English)》2014,53(32):8338-8342
Reproducible and controllable growth of nanostructures with well‐defined physical and chemical properties is a longstanding problem in nanoscience. A key step to address this issue is to understand their underlying growth mechanism, which is often entangled in the complexity of growth environments and obscured by rapid reaction speeds. Herein, we demonstrate that the evolution of size, surface morphology, and the optical properties of gold plasmonic nanostructures could be quantitatively intercepted by dynamic and stoichiometric control of the DNA‐mediated growth. By combining synchrotron‐based small‐angle X‐ray scattering (SAXS) with transmission electron microscopy (TEM), we reliably obtained quantitative structural parameters for these fine nanostructures that correlate well with their optical properties as identified by UV/Vis absorption and dark‐field scattering spectroscopy. Through this comprehensive study, we report a growth mechanism for gold plasmonic nanostructures, and the first semiquantitative revelation of the remarkable interplay between their morphology and unique plasmonic properties. 相似文献
966.
Po‐Yeng Feng Yi‐Hung Liu Prof. Tien‐Sung Lin Prof. Shie‐Ming Peng Prof. Ching‐Wen Chiu 《Angewandte Chemie (International ed. in English)》2014,53(24):6237-6240
Chemical reduction of a hydroxyphenyl‐substituted borane triggers a sequential electron‐ and intramolecular hydrogen‐atom‐transfer process to afford a hydridoborate phenoxide dianion. On the other hand, hydrogen‐atom abstraction of the borane leads to the isolation of a neutral borylated phenoxyl radical, which can be transformed to the corresponding benzoquinone borataalkene derivative by reduction with cobaltocene. 相似文献
967.
Dr. Itai Carmeli Dr. Karuppannan Senthil Kumar Omri Heifler Prof. Chanoch Carmeli Prof. Ron Naaman 《Angewandte Chemie (International ed. in English)》2014,53(34):8953-8958
Photosystem I (PSI) is one of the most studied electron transfer (ET) systems in nature; it is found in plants, algae, and bacteria. The effect of the system structure and its electronic properties on the electron transfer rate and yield was investigated for years in details. In this work we show that not only those system properties affect the ET efficiency, but also the electrons’ spin. Using a newly developed spintronic device and a technique which enables control over the orientation of the PSI monolayer relative to the device (silver) surface, it was possible to evaluate the degree and direction of the spin polarization in ET in PSI. We find high‐spin selectivity throughout the entire ET path and establish that the spins of the electrons being transferred are aligned parallel to their momenta. The spin selectivity peaks at 300 K and vanishes at temperatures below about 150 K. A mechanism is suggested in which the chiral structure of the protein complex plays an important role in determining the high‐spin selectivity and its temperature dependence. Our observation of high light induced spin dependent ET in PSI introduces the possibility that spin may play an important role in ET in biology. 相似文献
968.
Mapping of the Photoinduced Electron Traps in TiO2 by Picosecond X‐ray Absorption Spectroscopy 下载免费PDF全文
Dr. M. Hannelore Rittmann‐Frank Dr. Chris J. Milne Dr. Jochen Rittmann Dr. Marco Reinhard Dr. Thomas J. Penfold Prof. Majed Chergui 《Angewandte Chemie (International ed. in English)》2014,53(23):5858-5862
Titanium dioxide (TiO2) is the most popular material for applications in solar‐energy conversion and photocatalysis, both of which rely on the creation, transport, and trapping of charges (holes and electrons). The nature and lifetime of electron traps at room temperature have so far not been elucidated. Herein, we use picosecond X‐ray absorption spectroscopy at the Ti K‐edge and the Ru L3‐edge to address this issue for photoexcited bare and N719‐dye‐sensitized anatase and amorphous TiO2 nanoparticles. Our results show that 100 ps after photoexcitation, the electrons are trapped deep in the defect‐rich surface shell in the case of anatase TiO2, whereas they are inside the bulk in the case of amorphous TiO2. In the case of dye‐sensitized anatase or amorphous TiO2, the electrons are trapped at the outer surface. Only two traps were identified in all cases, with lifetimes in the range of nanoseconds to tens of nanoseconds. 相似文献
969.
Control of the Electronic Ground State on an Electron‐Transfer Copper Site by Second‐Sphere Perturbations 下载免费PDF全文
Marcos N. Morgada Dr. Luciano A. Abriata Ulises Zitare Dr. Damian Alvarez‐Paggi Prof. Daniel H. Murgida Prof. Alejandro J. Vila 《Angewandte Chemie (International ed. in English)》2014,53(24):6188-6192
The CuA center is a dinuclear copper site that serves as an optimized hub for long‐range electron transfer in heme–copper terminal oxidases. Its electronic structure can be described in terms of a σu* ground‐state wavefunction with an alternative, less populated ground state of πu symmetry, which is thermally accessible. It is now shown that second‐sphere mutations in the CuA containing subunit of Thermus thermophilus ba3 oxidase perturb the electronic structure, which leads to a substantial increase in the population of the πu state, as shown by different spectroscopic methods. This perturbation does not affect the redox potential of the metal site, and despite an increase in the reorganization energy, it is not detrimental to the electron‐transfer kinetics. The mutations were achieved by replacing the loops that are involved in protein–protein interactions with cytochrome c, suggesting that transient protein binding could also elicit ground‐state switching in the oxidase, which enables alternative electron‐transfer pathways. 相似文献
970.