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71.
72.
73.
J. I. Hoffman 《Fresenius' Journal of Analytical Chemistry》1934,96(3-4):135-137
Ohne Zusammenfassung 相似文献
74.
Chuanlei Liu Kurt Ungar Dylan Pierce Ian Hoffman Weihua Zhang 《Journal of Radioanalytical and Nuclear Chemistry》2017,312(3):471-478
In assistance of radionuclide measurements at Canada’s Comprehensive Nuclear-Test-Ban Treaty (CTBT) laboratory, a Geant4 Monte Carlo application has been developed in simulating a broad-energy germanium detector and calculating detection efficiencies. The detector model was optimized in a reliable and non-biased manner through simultaneous tuning on gap distance and detector dimension, and was validated over various realistic measurement scenarios. All work is based on a series of experiments which covers the typical energy range of gamma radiation in environmental analysis, and considers the variety of the CTBT sample type, dimension and distance-to-detector. In all cases, the predicted efficiencies are consistent with the empirical ones within 5%, with a typical deviation of 3% in majority. 相似文献
75.
Davydov R Osborne RL Shanmugam M Du J Dawson JH Hoffman BM 《Journal of the American Chemical Society》2010,132(42):14995-15004
Dehaloperoxidase (DHP) from Amphitrite ornata is a heme protein that can function both as a hemoglobin and as a peroxidase. This report describes the use of 77 K cryoreduction EPR/ENDOR techniques to study both functions of DHP. Cryoreduced oxyferrous [Fe(II)-O(2)] DHP exhibits two EPR signals characteristic of a peroxoferric [Fe(III)-O(2)(2-)] heme species, reflecting the presence of conformational substates in the oxyferrous precursor. (1)H ENDOR spectroscopy of the cryogenerated substates shows that H-bonding interactions between His N(ε)H and heme-bound O(2) in these conformers are similar to those in the β-chain of oxyferrous hemoglobin A (HbA) and oxyferrous myoglobin, respectively. Decay of cryogenerated peroxoferric heme DHP intermediates upon annealing at temperatures above 180 K is accompanied by the appearance of a new paramagnetic species with an axial EPR signal with g(⊥) = 3.75 and g(∥) = 1.96, characteristic of an S = 3/2 spin state. This species is assigned to Compound I (Cpd I), in which a porphyrin π-cation radical is ferromagnetically coupled with an S = 1 ferryl [Fe(IV)═O] ion. This species was also trapped by rapid freeze-quench of the ambient-temperature reaction mixture of ferric [Fe(III)] DHP and H(2)O(2). However, in the latter case Cpd I is reduced very rapidly by a nearby tyrosine to form Cpd ES [(Fe(IV)═O)(porphyrin)/Tyr(?)]. Addition of the substrate analogue 2,4,6-trifluorophenol (F(3)PhOH) suppresses formation of the Cpd I intermediate during annealing of cryoreduced oxyferrous DHP at 190 K but has no effect on the spectroscopic properties of the remaining cryoreduced oxyferrous DHP intermediates and kinetics of their decay. These observations indicate that substrate (i) binds to oxyferrous DHP outside of the distal pocket and (ii) can reduce Cpd I to Cpd II [Fe(IV)═O]. These assumptions are also supported by the observation that F(3)PhOH has only a small effect on the EPR properties of radiolytically cryooxidized and cryoreduced ferrous [Fe(II)] DHP. EPR spectra of cryoreduced ferrous DHP disclose the multiconformational nature of the ferrous DHP precursor. The observation and characterization of Cpds I, II, and ES in the absence and in the presence of F(3)PhOH provides definitive evidence of a mechanism involving consecutive one-electron steps and clarifies the role of all intermediates formed during turnover. 相似文献
76.
Soriaga RA Nguyen JM Albright TA Hoffman DM 《Journal of the American Chemical Society》2010,132(51):18014-18016
The addition of 4 equiv of LiN=C-t-Bu(2) to CrCl(3), MoCl(5), and WCl(6) in diethyl ether produced the complexes M(N=C-t-Bu(2))(4) (M = Cr, Mo, W). Single-crystal X-ray diffraction studies revealed that the molecules have flattened tetrahedral geometries with virtual D(2d) symmetry in the solid state. (1)H and (13)C NMR spectra indicated that the complexes are diamagnetic, and a qualitative MO analysis showed that the orthogonal π-donor and -acceptor orbitals of the ketimide ligand cooperatively split the d(xy) and d(z2) orbitals sufficiently to allow spin pairing in the d(xy) orbital. A more sophisticated quantum-mechanical analysis of Cr(N=C-t-Bu(2))(4) using density functional/molecular mechanics methods confirmed the qualitative analysis by showing that the singlet state is 27 kcal/mol more stable than the triplet state. 相似文献
77.
We report a mechanistic study of how flow and recirculation in a microreactor can be used to optimize the capture and release of stimuli-responsive polymer-protein reagents on stimuli-responsive polymer-grafted channel surfaces. Poly(N-isopropylacrylamide) (PNIPAAm) was grafted to polydimethylsiloxane (PDMS) channel walls, creating switchable surfaces where PNIPAAm-protein conjugates would adhere at temperatures above the lower critical solution temperature (LCST) and released below the LCST. A PNIPAAm-streptavidin conjugate that can capture biotinylated antibody-antigen targets was first characterized. The conjugate's immobilization and release were limited by mass transport to and from the functionalized PNIPAAm surface. Transport and adsorption efficiencies were dependent on the aggregate size of the PNIPAAm-streptavidin conjugate above the LCST and also were dependent on whether the conjugates were heated in the presence of the stimuli-responsive surface or pre-aggregated and then flowed across the surface. As conjugate size increased, through the addition of non-conjugated PNIPAAm, recirculation and mixing were shown to markedly improve conjugate immobilization compared to diffusion alone. Under optimized conditions of flow and reagent concentrations, approximately 60% of the streptavidin conjugate bolus could be captured at the surface and subsequently successfully released. The kinetic release profile sharpness was also strongly improved with recirculation and helical mixing. Finally, the concentration of protein-polymer conjugates could be achieved by continuous conjugate flow into the heated recirculator, allowing nearly linear enrichment of the conjugate reagent from larger volumes. This capability was shown with anti-p24 HIV monoclonal antibody reagents that were enriched over 5-fold using this protocol. These studies provide insight into the mechanism of smart polymer-protein conjugate capture and release in grafted channels and show the potential of this purification and enrichment module for processing diagnostic samples. 相似文献
78.
The zinc hydrazide complexes [EtZn(N(SiMe(3))NMe(2))](2), [EtZn(N(Me)NMe(2))](4), and Zn(3)Et(4)(N(Et)NMe(2))(2) were synthesized by allowing excess hydrazine, HN(R)NMe(2), to react with diethyl zinc. The product of the reaction between ZnEt(2) and HN(i-Pr)NMe(2)ortho-metalated 4-(dimethylamino)pyridine (DMAP) at room temperature, producing the complex Zn[(NC(5)H(3)-p-NMe(2))ZnEt(N(i-Pr)NMe(2))](2). At elevated temperatures, Zn(3)Et(4)(N(Et)NMe(2))(2) also ortho-metalated DMAP, but [EtZn(N(Me)NMe(2))](4) did not. Single-crystal X-ray diffraction studies revealed that the hydrazide ligands in [EtZn(N(SiMe(3))NMe(2))](2) act as bridging mono-hapto amide ligands, and in Zn(3)Et(4)(N(Et)NMe(2))(2) and Zn[(NC(5)H(3)-p-NMe(2))ZnEt(N(i-Pr)NMe(2))](2) the hydrazide ligands are di-hapto. 相似文献
79.
We introduce a new type of superconducting charge qubit that has a V-shaped energy spectrum and uses quantum interference to provide independently tunable qubit energy and coherent coupling to a superconducting cavity. Dynamic access to the strong coupling regime is demonstrated by tuning the coupling strength from less than 200 kHz to greater than 40 MHz. This tunable coupling can be used to protect the qubit from cavity-induced relaxation and avoid unwanted qubit-qubit interactions in a multiqubit system. 相似文献
80.
Schmidt B Mahmud G Soh S Kim SH Page T O'Halloran TV Grzybowski BA Hoffman BM 《Applied magnetic resonance》2011,40(4):415-425