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151.
Dr. Lingui Zhu Dr. Shasha Liu Dr. Justin T. Douglas Prof. Dr. Ryan A. Altman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12800-12805
The conversion of an alcohol‐based functional group, into a trifluoromethyl analogue is a desirable transformation. However, few methods are capable of converting O‐based electrophiles into trifluoromethanes. The copper‐mediated trifluoromethylation of benzylic xanthates using Umemoto’s reagent as the source of CF3 to form C? CF3 bonds is described. The method is compatible with an array of benzylic xanthates bearing useful functional groups. A preliminary mechanistic investigation suggests that the C? CF3 bond forms by reaction of the substrate with in situ generated CuCF3 and CuOTf. Further evidence suggests that the reaction could proceed via a radical cation intermediate. 相似文献
152.
In practical applications, information about the accuracy or ‘fidelity’ of alternative surrogate systems may be ambiguous and difficult to determine. To address this problem, we propose to treat surrogate system fidelity level as a categorical factor in optimal response surface design. To design the associated experiments, we apply the Expected Integrated Mean Squared Error optimal design criterion, which takes into account both variance and bias errors. The performance of the proposed design was compared using three test cases to four types of alternatives using the Empirical Integrated Squared Error. Because of its ability to foster relatively accurate predictions, the proposed design is recommended in fidelity experimental design, particularly when the experimenters lack sufficient information about the fidelity levels of surrogate systems. The method was applied to the case of intraday trading optimization in which data were collected from the Taiwan Futures Exchange. We also calculated the implied volatility from the Merton's Jump‐diffusion model via the fast Fourier transform algorithm with three different models of varying fidelity levels. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
153.
Ryan Gianatassio Shuhei Kawamura Cecil L Eprile Klement Foo Jason Ge Aaron C. Burns Michael R. Collins Phil S. Baran 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(37):10009-10013
A simple method to convert readily available carboxylic acids into sulfinate salts by employing an interrupted Barton decarboxylation reaction is reported. A medicinally oriented panel of ten new sulfinate reagents was created using this method, including a key trifluoromethylcyclopropanation reagent, TFCS‐Na. The reactivity of six of these salts towards C H functionalization was field‐tested using several different classes of heterocycles. 相似文献
154.
Leia Fan Elaine Jian Wen-Chun Chang Yvonne Wu Jason Lin Andy Tseng Jessica Tseng Renee Wan Annie Yu Eric Lee 《Electrophoresis》2022,43(21-22):2227-2233
Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery. 相似文献
155.
Ryan M. Tipker Jake A. Muldoon Daniel H. Pham Balazs R. Varga Russell P. Hughes David S. Glueck Gary J. Balaich Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202110753
Tetrahedral main-group compounds are normally configurationally stable, but P-epimerization of the chiral phosphiranium cations syn- or anti-[Mes*P(Me)CH2CHPh][OTf] (Mes*=2,4,6-(t-Bu)3C6H2) occurred under mild conditions at 60 °C in CD2Cl2, resulting in isomerization to give a syn-enriched equilibrium mixture. Ion exchange with excess [NBu4][Δ-TRISPHAT] (Δ-TRISPHAT=Δ-P(o-C6Cl4O2)3) followed by chromatography on silica removed [NBu4][OTf] and gave mixtures of syn- and anti-[Mes*P(Me)CH2CHPh][Δ-TRISPHAT]?x[NBu4][Δ-TRISPHAT]. NMR spectroscopy showed that isomerization proceeded with epimerization at P and retention at C. DFT calculations are consistent with a mechanism involving P-C cleavage to yield a hyperconjugation-stabilized carbocation, pyramidal inversion promoted by σ-interaction of the P lone pair with the neighboring β-carbocation, and ring closure with inversion of configuration at P. 相似文献
156.
Dr. Zijie Zhang Dr. Jiuxing Li Jimmy Gu Ryan Amini Hannah D. Stacey Jann C. Ang Dawn White Prof. Dr. Carlos D. M. Filipe Prof. Dr. Karen Mossman Prof. Dr. Matthew S. Miller Prof. Dr. Bruno J. Salena Prof. Dr. Deborah Yamamura Dr. Payel Sen Prof. Dr. Leyla Soleymani Prof. Dr. John D. Brennan Prof. Dr. Yingfu Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(15):e202200078
We report on a unique DNA aptamer, denoted MSA52, that displays universally high affinity for the spike proteins of wildtype SARS-CoV-2 as well as the Alpha, Beta, Gamma, Epsilon, Kappa, Delta and Omicron variants. Using an aptamer pool produced from round 13 of selection against the S1 domain of the wildtype spike protein, we carried out one-round SELEX experiments using five different trimeric spike proteins from variants, followed by high-throughput sequencing and sequence alignment analysis of aptamers that formed complexes with all proteins. A previously unidentified aptamer, MSA52, showed Kd values ranging from 2 to 10 nM for all variant spike proteins, and also bound similarly to variants not present in the reselection experiments. This aptamer also recognized pseudotyped lentiviruses (PL) expressing eight different spike proteins of SARS-CoV-2 with Kd values between 20 and 50 pM, and was integrated into a simple colorimetric assay for detection of multiple PL variants. This discovery provides evidence that aptamers can be generated with high affinity to multiple variants of a single protein, including emerging variants, making it well-suited for molecular recognition of rapidly evolving targets such as those found in SARS-CoV-2. 相似文献
157.
158.
We describe a new type of Fourier transform (FT) interferometer in which the tunable optical delay between the two arms is realized by using a continuously variable slow-light medium instead of a moving arm as in a conventional setup. The spectral resolution of such a FT interferometer exceeds that of a conventional setup of comparable size by a factor equal to the maximum group index of the slow-light medium. The scheme is experimentally demonstrated by using a rubidium atomic vapor cell as the tunable slow-light medium, and the spectral resolution is enhanced by a factor of approximately 100. 相似文献
159.
Warburton RE McCarthy A Wallace AM Hernandez-Marin S Hadfield RH Nam SW Buller GS 《Optics letters》2007,32(15):2266-2268
We demonstrate subcentimeter depth profiling at a stand off distance of 330 m using a time-of-flight approach based on time-correlated single-photon counting. For the first time to our knowledge, the photon-counting time-of-flight technique was demonstrated at a wavelength of 1550 nm using a superconducting nanowire single-photon detector. The performance achieved suggests that a system using superconducting detectors has the potential for low-light-level and eye-safe operation. The system's instrumental response was 70 ps full width at half-maximum, which meant that 1 cm surface-to-surface resolution could be achieved by locating the centroids of each return signal. A depth resolution of 4 mm was achieved by employing an optimized signal-processing algorithm based on a reversible jump Markov chain Monte Carlo method. 相似文献
160.
Dr. Andrea Previtali Dr. Wei He Dr. Alessandra Forni Dr. Daniele Malpicci Dr. Elena Lucenti Dr. Daniele Marinotto Prof. Lucia Carlucci Prof. Pierluigi Mercandelli Dr. Marco Aldo Ortenzi Prof. Giancarlo Terraneo Dr. Chiara Botta Prof. Ryan Tsz Kin Kwok Dr. Jacky Wing Yip Lam Prof. Ben Zhong Tang Prof. Elena Cariati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(67):16690-16700
Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation-dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different species has been followed by thermal and X-ray diffraction analyses and the emissive features interpreted through structural results and DFT/TDDFT calculations. Particularly intriguing is the polymorph TTPyr(HT), serendipitously obtained at high temperature but stable also at room temperature, whose non-centrosymmetric structure guarantees an SHG efficiency 10 times higher than that of standard urea. Its crystal packing, where only the TT units are strongly rigidified by π-π stacking interactions while the Pyr moieties possess partial conformational freedom, is responsible for the observed dual fluorescence. The potentialities of TTPyr for bioimaging have been successfully established. 相似文献