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141.
Ru Yao David Beriashvili Wenxiao Zhang Shuai Li Adil Safeer Andrei Gurinov Antal Rockenbauer Yin Yang Yuguang Song Marc Baldus Yangping Liu 《Chemical science》2022,13(47):14157
Cellular dynamic nuclear polarization (DNP) has been an effective means of overcoming the intrinsic sensitivity limitations of solid-state nuclear magnetic resonance (ssNMR) spectroscopy, thus enabling atomic-level biomolecular characterization in native environments. Achieving DNP signal enhancement relies on doping biological preparations with biradical polarizing agents (PAs). Unfortunately, PA performance within cells is often limited by their sensitivity to the reductive nature of the cellular lumen. Herein, we report the synthesis and characterization of a highly bioresistant and hydrophilic PA (StaPol-1) comprising the trityl radical OX063 ligated to a gem-diethyl pyrroline nitroxide via a rigid piperazine linker. EPR experiments in the presence of reducing agents such as ascorbate and in HeLa cell lysates demonstrate the reduction resistance of StaPol-1. High DNP enhancements seen in small molecules, proteins and cell lysates at 18.8 T confirm that StaPol-1 is an excellent PA for DNP ssNMR investigations of biomolecular systems at high magnetic fields in reductive environments.The new polarizing agent combines extraordinarily high bioresistance with excellent DNP performance at high magnetic fields and provides uniform DNP enhancement of 183 at 18.8 T for [13C, 15N]-ubiquitin in HeLa cell lysates. 相似文献
142.
The pine leaves which are an agricultural residue were used in its natural form as biosorbent for the removal of Acid Yellow 220 (AY 220) dye from aqueous solutions. The sorption experiments were carried out as a function of solution pH, biosorbent dosage, biosorbent size, dye concentration, temperature, contact time and ionic strength. The sorption isotherms closely followed the Langmuir model. The monolayer sorption capacity of the pine leaves for AY 220 was found as 40.00 mg g− 1. It was shown that pseudo-second order equation could best describe the sorption kinetics. The thermodynamic data indicated that the sorption system was spontaneous, endothermic and physical process. Based on the results of present investigation, the pine leaves could be used as a suitable alternative biosorbent for the elimination of AY 220 from aqueous solutions. 相似文献
143.
Solid-phase extraction (SPE) columns packed with materials based on molecularly imprinted polymers (MIPs) were used to develop selective separation and preconcentration for Ni(II) ion from aqueous solutions. SPE is more rapid, simple and economical method than the traditional liquid-liquid extraction. MIPs were used as column sorbent to increase the grade of selectivity in SPE columns. In this study, we have developed a polymer obtained by imprinting with Ni(II) ion as a ion-imprinted SPE sorbent. For this purpose, NI(II)-methacryloylhistidinedihydrate (MAH/Ni(II)) complex monomer was synthesized and polymerized with cross-linking ethyleneglycoldimethacrylate to obtain [poly(EGDMA-MAH/Ni(II))]. Then, Ni(II) ions were removed from the polymer getting Ni(II) ion-imprinted sorbent. The MIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.3 to 25 ng/ml and the detection limit was 0.3 ng/ml (3 s) for flame atomic absorption spectrometry (FAAS). Ni(II) ion-imprinted microbeads can be used several times without considerable loss of adsorption capacity. When the adsorption capacity of nickel imprinted microbeads were compared with non-imprinted microbeads, nickel imprinted microbeads have higher adsorption capacity. The Kd (distribution coefficient) values for the Ni(II)-imprinted microbeads show increase in Kd for Ni(II) with respect to both Kd values of Zn(II), Cu(II) and Co(II) ions and non-imprinted polymer. During that time Kd decreases for Zn(II), Cu(II) and Co(II) ions and the k′ (relative selectivity coefficient) values which are greater than 1 for imprinted microbeads of Ni(II)/Cu(II), Ni(II)/Zn(II) and Ni(II)/Co(II) are 57.3, 53.9, and 17.3, respectively. Determination of Ni(II) ion in sea water showed that the interfering matrix had been almost removed during preconcentration. The column was good enough for Ni determination in matrixes containing similar ionic radii ions such as Cu(II), Zn(II) and Co(II). 相似文献
144.
In this paper, we are concerned with a show the existence of a entropy solution to the obstacle problem associated with the equation of the type :$\begin{cases}Au+g(x,u,∇u) = f & {\rm in} & Ω \\ u=0 & {\rm on} & ∂Ω \end{cases}$where $\Omega$ is a bounded open subset of $\;\mathbb{R}^{N}$, $N\geq 2$, $A\,$ is an operator of Leray-Lions type acting from $\; W_{0}^{1,\overrightarrow{p}(.)} (\Omega,\ \overrightarrow{w}(.))\;$ into its dual $\; W_{0}^{-1,\overrightarrow{p}'(.)} (\Omega,\ \overrightarrow{w}^*(.))$ and $\,L^1\,-\,$deta. The nonlinear term $\;g\,$: $\Omega\times \mathbb{R}\times \mathbb{R}^{N}\longrightarrow \mathbb{R} $ satisfying only some growth condition. 相似文献
145.
Matni A Boubekeur L Grosshans P Mézailles N Bernardinelli G Le Floch P Geoffroy M 《Magnetic resonance in chemistry : MRC》2007,45(12):1011-1017
Bis-iminophosphoranes containing various types of linkers between two R3P==N moieties were electrochemically oxidized at controlled potential in situ in the electron spin resonance (ESR) cavity. For linkers constituted of phenylenes, conjugated phenylenes or merely a dicyanoethylenic bond, this oxidation led to well-resolved ESR spectra which were characterized by their g values and by their 1H, 14N and 31P isotropic hyperfine constants. These coupling constants agree with those calculated by DFT for the corresponding cation radicals. Experimental and theoretical results clearly indicate that in these species the unpaired electron is mostly delocalized on the bridge and on the nitrogen atoms while the spin density on the phosphorus atoms is particularly small. Cyclic voltammetry and ESR spectra show that the nature of the bridge between the two iminophosphoranes considerably influences the oxidation potential of the compound as well as the stability of the radical cation. Information about the conformation of the precursor containing two Ph3P==N moieties separated by a --C(CN)==C(CN)--group was obtained from its crystal structure. 相似文献
146.
Asymmetric organocatalytic sulfa-Michael reactions give access to enantiomerically enriched sulfur containing adducts that can be used as valuable chiral building blocks. A variety of chalcone derivatives were allowed to react with methyl thioglycolate under optimized conditions, in the presence of a bifunctional quinine derived sterically encumbered squaramide organocatalyst, giving rise to excellent stereoselectivities, up to 99%?ee. The designed catalyst system proved to be efficient even at gram scale and under milder reaction conditions. 相似文献
147.
A new approach, combining metal coordination with the molecular imprinting technique, was developed to prepare affinity materials. Magnetic poly(glycidyl methacrylate) microspheres in monosize form were used for specific recognition toward the target protein. The magnetic poly(glycidyl methacrylate) microspheres were prepared by dispersion polymerization in the presence of magnetite nanopowder. Surface imprinted magnetic poly(glycidyl methacrylate) microspheres based on metal coordination were prepared and used for the selective recognition of human serum albumin. Iminodiacetic acid was used as the metal coordinating agent and human serum albumin was anchored by Cu2+ ions on the surface of magnetic poly(glycidyl methacrylate) microspheres by metal coordination. The magnetic poly(glycidyl methacrylate) microspheres were coated with a polymer formed by condensation of tetraethyl orthosilicate and 3‐aminopropyltrimethoxysilane. The human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres were characterized by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy and particle size analysis. The maximum adsorption capacity of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres was 37.7 mg/g polymer at pH 6.0. The selectivity experiments of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres prepared with different concentrations in the presence of lysozyme, bovine serum albumin and cytochrome C were performed in order to determine the relative selectivity coefficients. 相似文献
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