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101.
环境友好型纳米生物传感器能够提高传统生物分子传感器的检测性能,在实际应用中具有重要的应用价值。本研究以胆碱氧化酶(ChOx)为模板,在室温(25 ℃)下通过矿化作用制备了一种ChOx功能化的室温磷光(RTP)量子点(QDs)(ChOx RTP QDs)纳米生物传感器,并利用ChOx与氯化胆碱的特异性酶-底物反应和光诱导的电子转移(PIET)实现了对氯化胆碱(Cho)的RTP定量检测。该纳米生物传感器对氯化胆碱检测的线性范围为0.05~20 mmol/L,检出限为0.02 mmol/L。该方法基于QDs的RTP性质,可以有效地避免生物样品背景荧光的干扰,且无需复杂的样品前处理过程,因此该方法较适合于生物样品中氯化胆碱的定量检测。 相似文献
102.
103.
High‐Energy Long‐Lived Mixed Frenkel–Charge‐Transfer Excitons: From Double Stranded (AT)n to Natural DNA 下载免费PDF全文
Dr. Ignacio Vayá Dr. Johanna Brazard Dr. Miquel Huix‐Rotllant Dr. Arun K. Thazhathveetil Prof. Frederick D. Lewis Dr. Thomas Gustavsson Prof. Dr. Irene Burghardt Dr. Roberto Improta Dr. Dimitra Markovitsi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4904-4914
The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV‐induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine–thymine double‐stranded structures (AT)n. Fluorescence measurements on (AT)n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time‐dependent (TD)‐DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine‐to‐thymine charge‐transfer states. Emission from such high‐energy long‐lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π–π* states (≥0.1). An increase in the size of the system quenches π–π* fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π–π* and charge‐transfer states. Subsequently, we identify the common features between the HELM states of (AT)n structures with those reported previously for alternating (GC)n: high emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π–π* states, giving rise to delayed fluorescence. 相似文献
104.
Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS3O10]− in A[HS3O10] (A=Na,K, Rb) 下载免费PDF全文
Lisa Verena Schindler Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13865-13870
The reaction of Na2SO4 and K2SO4 with fuming sulfuric acid (65 % SO3) yielded colorless extremely sensitive crystals of Na[HS3O10] (monoclinic; P21/n (No. 14); Z=4; a=707.36(2), b=1378.56(4), c=848.10(3) pm; β=94.817(1)°; V=824.09(4) ? 106 pm3) and K[HS3O10] (orthorhombic; Pccn (No. 56); Z=4; a=1057.16(3), b=807.81(2), c=897.57(2) pm; V=766.51(3) ? 106 pm3). The analogous rubidium compound Rb[HS3O10] (orthorhombic; Pnma (No. 62); Z=4; a=891.43(3), b=1095.34(4), c=839.37(3) pm; V=819.58(5) ? 106 pm3) originates from the reaction of Rb2CO3 and SO3. All of the different structures contain the hitherto unknown anion [HS3O10]? and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS3O10]?. The preparation of the [HS3O10]? anion can be seen as an important milestone on our way to the still elusive polysulfuric acids. 相似文献
105.
Inside Back Cover: Deciphering a Nanocarbon‐Based Artificial Peroxidase: Chemical Identification of the Catalytically Active and Substrate‐Binding Sites on Graphene Quantum Dots (Angew. Chem. Int. Ed. 24/2015) 下载免费PDF全文
106.
Dr. Chongyang Zhu Prof. Feng Xu Dr. Ling Zhang Prof. Minli Li Prof. Jing Chen Dr. Shuhong Xu Dr. Guangguang Huang Dr. Wenhao Chen Prof. Litao Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(22):7357-7362
Black phosphorus quantum dots (BPQDs) have been prepared by a high turbulent shear rate generated from a household kitchen blender. A layer‐by‐layer disintegration mechanism of bulk BP crystals is suggested. As‐synthesized BPQDs have shown excellent humidity sensing and photothermal converting properties. Importantly, this work not only explores potential applications for the BPQDs but also provides a successful paradigm for preparing the QDs of other layered materials. 相似文献
107.
Computational Chemistry to the Rescue: Modern Toolboxes for the Assignment of Complex Molecules by GIAO NMR Calculations
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Dr. Nicolas Grimblat Dr. Ariel M. Sarotti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12246-12261
The calculations of NMR properties of molecules using quantum chemical methods have deeply impacted several branches of organic chemistry. They are particularly important in structural or stereochemical assignments of organic compounds, with implications in total synthesis, stereoselective reactions, and natural products chemistry. In studying the evolution of the strategies developed to support (or reject) a structural proposal, it becomes clear that the most effective and accurate ones involve sophisticated procedures to correlate experimental and computational data. Owing to their relatively high mathematical complexity, such calculations (CP3, DP4, ANN‐PRA) are often carried out using additional computational resources provided by the authors (such as applets or Excel files). This Minireview will cover the state‐of‐the‐art of these toolboxes in the assignment of organic molecules, including mathematical definitions, updates, and discussion of relevant examples. 相似文献
108.
Commentary on “Caged Phosphate and the Slips and Misses in Determination of Quantum Yields for Ultraviolet‐A‐Induced Photouncaging” by G. Gasser and Co‐Workers 下载免费PDF全文
109.
Localization and Dynamics of Long‐Lived Excitations in Colloidal Semiconductor Nanocrystals with Dual Quantum Confinement 下载免费PDF全文
Dr. Su Liu Dr. Nicholas J. Borys Prof. Sameer Sapra Prof. Alexander Eychmüller Prof. John M. Lupton 《Chemphyschem》2015,16(8):1663-1669
Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non‐radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha′s rule. Using nanosecond time‐resolved spectroscopy of QDQW CdSe/ZnS onion‐like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non‐radiative relaxation of the higher‐energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher‐energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long‐lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core‐only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well‐defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady‐state or ultrafast spectroscopy. 相似文献
110.
Dr. Ulrich P. Preiss Dr. Dzmitry H. Zaitsau Dr. Witali Beichel Dr. Daniel Himmel Dr. Alexander Higelin Dr. Klaus Merz Niklas Caesar Prof. Dr. Sergey P. Verevkin 《Chemphyschem》2015,16(13):2890-2898
New measurements of vaporization enthalpies for 15 1:1 ionic liquids are performed by using a quartz‐crystal microbalance. Collection and analysis of 33 available crystal structures of organic salts, which comprise 13 different cations and 12 anions, is performed. Their dissociation lattice enthalpies are calculated by a combination of experimental and quantum chemical quantities and are divided into the relaxation and Coulomb components to give an insight into elusive short‐range interaction enthalpies. An empirical equation is developed, based on interaction‐specific Hirshfeld surfaces and solvation enthalpies, which enables the estimation of the lattice enthalpy by using only the crystal‐structure data. 相似文献