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991.
Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects 下载免费PDF全文
Ming Gong Shan Zhou Jiahua Hu Min Zhi Yang You Song Bai Prof. Jun Jiang Prof. Qun Zhang Prof. Xiaojun Wu Prof. Yujie Xiong 《Angewandte Chemie (International ed. in English)》2014,53(12):3205-3209
The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O2 to generate a species that behaves like singlet O2 both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO2 supports. Driven by the Schottky junction, the TiO2 supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO2 under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O2 activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO2 hybrid structures. 相似文献
992.
Dr. Jae‐Il Jung Dr. Hu Young Jeong Jang‐Soo Lee Dr. Min Gyu Kim Prof. Dr. Jaephil Cho 《Angewandte Chemie (International ed. in English)》2014,53(18):4582-4586
La0.3(Ba0.5Sr0.5)0.7Co0.8Fe0.2O3?δ is a promising bifunctional perovskite catalyst for the oxygen reduction reaction and the oxygen evolution reaction. This catalyst has circa 10 nm‐scale rhombohedral LaCoO3 cobaltite particles distributed on the surface. The dynamic microstructure phenomena are attributed to the charge imbalance from the replacement of A‐site cations with La3+ and local stress on Co‐site sub‐lattice with the cubic perovskite structure. 相似文献
993.
Fan Shi Aaron M. Coffey Assist. Prof. Kevin W. Waddell Assist. Prof. Eduard Y. Chekmenev Assoc. Prof. Boyd M. Goodson 《Angewandte Chemie (International ed. in English)》2014,53(29):7495-7498
A novel variant of an iridium‐based organometallic catalyst was synthesized and used to enhance the NMR signals of pyridine in a heterogeneous phase by immobilization on polymer microbead solid supports. Upon administration of parahydrogen (pH2) gas to a methanol mixture containing the HET‐SABRE catalyst particles and the pyridine, up to fivefold enhancements were observed in the 1H NMR spectra after sample transfer to high field (9.4 T). Importantly, enhancements were not due to any residual catalyst molecules in solution, thus supporting the true heterogeneity of the SABRE process. Further significant improvements may be expected by systematic optimization of experimental parameters. Moreover, the heterogeneous catalyst is easy to separate and recycle, thus opening a door to future potential applications varying from spectroscopic studies of catalysis, to imaging metabolites in the body without concern of contamination from expensive and potentially toxic metal catalysts or accompanying organic molecules. 相似文献
994.
Jinrong Yang Dr. Guosheng Shi Dr. Yusong Tu Prof. Haiping Fang 《Angewandte Chemie (International ed. in English)》2014,53(38):10190-10194
Recent experiments have shown the coexistence of both large unoxidized and oxidized regions on graphene oxide (GO), but the underlying mechanism for the formation of the GO atomic structure remains unknown. Now, using density functional calculations, 52 oxidation pathways for local pyrene structures on GO were identified, and a kinetic profile for graphene oxidation with a high correlation between oxidation loci was proposed, which is different from the conventional view, which entails a random distribution of oxidation loci. The high correlation is an essential nature of graphene oxidation processes and can be attributed to three crucial effects: 1) breaking of delocalized π bonds, 2) steric hindrance, and 3) hydrogen‐bond formation. This high correlation leads to the coexistence of both large unoxidized and oxidized regions on GO. Interestingly, even in oxidized regions on GO, some small areas of sp2‐hybridized domains, similar to “islands”, can persist because of steric effects. 相似文献
995.
Aram Hong Chang Min Choi Han Jun Eun Changseop Jeong Prof. Jiyoung Heo Prof. Nam Joon Kim 《Angewandte Chemie (International ed. in English)》2014,53(30):7805-7808
The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations. 相似文献
996.
Sulfonamide‐Promoted Palladium(II)‐Catalyzed Alkylation of Unactivated Methylene C(sp3)H Bonds with Alkyl Iodides 下载免费PDF全文
Kai Chen Prof. Dr. Bing‐Feng Shi 《Angewandte Chemie (International ed. in English)》2014,53(44):11950-11954
The alkylation of unactivated β‐methylene C(sp3)? H bonds of α‐amino acid substrates with a broad range of alkyl iodides using Pd(OAc)2 as the catalyst is described. The addition of NaOCN and 4‐Cl‐C6H4SO2NH2 was found to be crucial for the success of this transformation. The reaction is compatible with a diverse array of functional groups and proceeds with high diastereoselectivity. Furthermore, various β,β‐hetero‐dialkyl‐ and β‐alkyl‐β‐aryl‐α‐amino acids were prepared by sequential C(sp3)? H functionalization of an alanine‐derived substrate, thus providing a versatile strategy for the stereoselective synthesis of unnatural β‐disubstituted α‐amino acids. 相似文献
997.
Yingbo Shi Baochao Yang Shujun Cai Prof. Dr. Shuanhu Gao 《Angewandte Chemie (International ed. in English)》2014,53(36):9539-9543
The total synthesis of gracilamine, a pentacyclic Amaryllidaceae alkaloid, was achieved from simple building blocks. The synthesis features a mild photo‐Nazarov reaction, intramolecular 1,4‐addition, and an intramolecular Mannich reaction. This approach not only confirms the C6 stereochemistry of natural gracilamine, and also provides a novel solution to prepare its derivatives and structurally related natural products. 相似文献
998.
Lysosomal pH Rise during Heat Shock Monitored by a Lysosome‐Targeting Near‐Infrared Ratiometric Fluorescent Probe 下载免费PDF全文
Dr. Qiongqiong Wan Prof. Dr. Suming Chen Prof. Dr. Wen Shi Lihong Li Prof. Dr. Huimin Ma 《Angewandte Chemie (International ed. in English)》2014,53(41):10916-10920
Heat stroke is a life‐threatening condition, featuring a high body temperature and malfunction of many organ systems. The relationship between heat shock and lysosomes is poorly understood, mainly because of the lack of a suitable research approach. Herein, by incorporating morpholine into a stable hemicyanine skeleton, we develop a new lysosome‐targeting near‐infrared ratiometric pH probe. In combination with fluorescence imaging, we show for the first time that the lysosomal pH value increases but never decreases during heat shock, which might result from lysosomal membrane permeabilization. We also demonstrate that this lysosomal pH rise is irreversible in living cells. Moreover, the probe is easy to synthesize, and shows superior overall analytical performance as compared to the existing commercial ones. This enhanced performance may enable it to be widely used in more lysosomal models of living cells and in further revealing the mechanisms underlying heat‐related pathology. 相似文献
999.
PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles 下载免费PDF全文
Tomoki Yoneda Young Mo Sung Dr. Jong Min Lim Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2014,53(48):13169-13173
Reductive metalation of [44]decaphyrin with [Pd2(dba)3] provided a Hückel aromatic [46]decaphyrin PdII complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin PdII complex. In CH2Cl2 solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin PdII complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three PdII complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date. 相似文献
1000.
Two‐Component Supramolecular Gels Derived from Amphiphilic Shape‐Persistent Cyclo[6]aramides for Specific Recognition of Native Arginine 下载免费PDF全文
Youzhou He Min Xu Rongzhao Gao Xiaowei Li Fengxue Li Xuedan Wu Prof. Dingguo Xu Dr. Huaqiang Zeng Prof. Lihua Yuan 《Angewandte Chemie (International ed. in English)》2014,53(44):11834-11839
A unique supramolecular two‐component gelation system was constructed from amphiphilic shape‐persistent cyclo[6]aramides and diethylammonium chloride (or triethylammonium chloride). This system has the ability to discriminate native arginine from 19 other amino acids in a specific fashion. Cyclo[6]aramides show preferential binding for the guanidinium residue over ammonium groups. This specificity was confirmed by both experimental results and theoretical simulations. These results demonstrated a new modular displacement strategy, exploring the use of species‐binding hydrogen‐bonded macrocyclic foldamers for the construction of two‐component gelation systems for selective recognition of native amino acids by competitive host–guest interactions. This strategy may be amenable to developing a variety of functional two‐component gelators for specific recognition of various targeted organic molecular species. 相似文献