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41.
The mass spectra of neopentyl alcohol, bromide and chloride and some 13C and 2H labelled analogues have been studied. Most fragmentations of the molecular ions of these compounds occur by simple bond cleavages and do not involve rearrangement before fragmentation. We propose that in the [M ? CH3]+ fragment ions, seven of the eight hydrogen atoms and all four carbon atoms are involved in randomisation when an ethylene molecule is ejected. The eighth hydrogen atom (which comes from a methyl group) is probably associated with the heteroatom. The neopentylcation, observed only in the mass spectrum of the bromide, fragments mainly by loss of an ethylene molecule, also containing randomly selected hydrogen and carbon atoms. The [C4H7]+ ion also was observed to undergo complete atom scrambling. 相似文献
42.
Treatment of several divalent transition-metal trifluoromethanesulfonates [M(II)(OTf)2; M(II) = Mn, Co, Ni] with [NEt4][Tp*Fe(III)(CN)3] [Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] in DMF affords three isostructural rectangular clusters of {[Tp*Fe(III)(CN)3M(II)(DMF)4]2[OTf]2} x 2DMF (M(II) = Mn, 3; Co, 4; Ni, 5) stoichiometry. Magnetic studies of 3-5 indicate that the Tp*Fe(CN)3(-) centers are highly anisotropic and exhibit antiferromagnetic (3 and 4) and ferromagnetic (5) exchange to afford S = 4, 2, and 3 spin ground states, respectively. ac susceptibility measurements suggest that 4 and 5 exhibit incipient single-molecule magnetic behavior below 2 K. 相似文献
43.
Mohammed I. Jeraal Nicholas Holmes Geoffrey R. Akien Richard A. Bourne 《Tetrahedron》2018,74(25):3158-3164
Reaction optimisation and understanding is fundamental for process development and is achieved using a variety of techniques. This paper explores the use of self-optimisation and experimental design as a tandem approach to reaction optimisation. A Claisen-Schmidt condensation was optimised using a branch and fit minimising algorithm, with the resulting data being used to fit a response surface model. The model was then applied to find new responses for different metrics, highlighting the most important for process development purposes. 相似文献
44.
Xuan Thinh Duong Irina Holmes Ji Li Brett D. Wick Dongyong Yang 《Journal of Functional Analysis》2019,276(4):1007-1060
In this paper we establish the characterization of the weighted BMO via two weight commutators in the settings of the Neumann Laplacian on the upper half space and the reflection Neumann Laplacian on with respect to the weights associated to and respectively. This in turn yields a weak factorization for the corresponding weighted Hardy spaces, where in particular, the weighted class associated to is strictly larger than the Muckenhoupt weighted class and contains non-doubling weights. In our study, we also make contributions to the classical Muckenhoupt–Wheeden weighted Hardy space (BMO space respectively) by showing that it can be characterized via the area function (Carleson measure respectively) involving the semigroup generated by the Laplacian on and that the duality of these weighted Hardy and BMO spaces holds for Muckenhoupt weights with while the previously known related results cover only . We also point out that this two weight commutator theorem might not be true in the setting of general operators L, and in particular we show that it is not true when L is the Dirichlet Laplacian on . 相似文献
45.
Alfred Schmidpeter Angela Willhalm Jürgen Kroner Roberta O. Day Joan M. Holmes Robert R. Holmes 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):495-498
Abstract Phosphamethincyanines prepared in 1964 by Dimroth and Hoffmann were among the first compounds with two-coordinate phosphorus. They are special cases of 2-phospha-allylic cations. Simple representatives of this type become available from the reaction of imidoyl chlorides with tris(trimethylsily1)phosphane. 相似文献
46.
J. Sarah Caygill Stuart D. Collyer Joanne L. Holmes Frank Davis Séamus P. J. Higson 《Electroanalysis》2013,25(11):2445-2452
We describe the use of cobalt phthalocyanine as a mediator to improve the sensitivity for the electrochemical detection of TNT. Commercial screen‐printed electrodes containing cobalt phthalocyanine were employed for determination of TNT. Improved sensitivities compared to screen‐printed carbon electrodes without phthalocyanine were observed, current response for cyclic voltammetric measurements at modified electrodes being at least double that of unmodified electrodes. A synergistic effect between oxygen and TNT reduction was also observed. Correlation between TNT concentrations and sensor output was observed between 0–200 µM TNT. Initial proof‐of‐concept experiments combining electrochemical determinations, with the use of an air‐sampling cyclone, are also reported. 相似文献
47.
Zeolite Y was systematically synthesized from Ahoko Nigerian kaolin in a conventional hydrothermal system using novel metakaolinization technique. The effect of aging on the formation of zeolite phase was investigated during the course of the synthesis. A rapidly processed metakaolin at a temperature of 600°C and exposure time of 50 minutes, which is capable of reducing the energy and cost of producing it was used to study the synthesis of zeolite Y. It was found that aging conditions play a prominent role in the preparation of zeolite Y from Ahoko metakaolin. Aging played a significant role by increasing the crystallinity of the final product even though zeolite Y was obtain without aging. The outcome of zeolite Y synthesized from Ahoko kaolin in 9 hours at 100°C was different from most reports on the synthesis of zeolite Y from kaolin where longing time (72 hours) of crystallization are reported. 相似文献
48.
Oliver Bleher Aline Schindler Meng-Xin Yin Andrew B. Holmes Peter B. Luppa Günter Gauglitz Günther Proll 《Analytical and bioanalytical chemistry》2014,406(14):3305-3314
Autoimmune diseases are characterized by the presence of autoantibodies in serum of affected patients. The heterogeneity of autoimmune relevant antigens creates a variety of different antibodies, which requires a simultaneous detection mode. For this reason, we developed a tool for parallelized, label-free, optical detection that accomplishes the characterization of multiple antigen–antibody interactions within a single measurement on a timescale of minutes. Using 11-aminoundecyltrimethoxysilane, we were able to immobilize proteinogenic antigens as well as an amino-functionalized cardiolipin on a glass surface. Assay conditions were optimized for serum measurements with a single spot antigen chip on a single spot 1-λ detection system. Minimized background signal allows a differentiation between patients and healthy controls with a good sensitivity and specificity. Applying polarized imaging reflectometric interference spectroscopy, we evaluated samples from three APS patients and three control subjects for this proof-of-principle and already obtained good results for β2-glycoprotein I and cardiolipin. 相似文献
49.
The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions
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Dr. Gillian Collins Michael Schmidt Dr. Colm O'Dwyer Prof. Justin D. Holmes Dr. Gerard P. McGlacken 《Angewandte Chemie (International ed. in English)》2014,53(16):4142-4145
The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions. 相似文献
50.
Investigating sorption-driven dissolved organic matter fractionation by multidimensional fluorescence spectroscopy and PARAFAC 总被引:1,自引:0,他引:1
Banaitis MR Waldrip-Dail H Diehl MS Holmes BC Hunt JF Lynch RP Ohno T 《Journal of colloid and interface science》2006,304(1):271-276
Soil organic matter is involved in many ecosystem processes, such as nutrient supply, metal solubilization, and carbon sequestration. This study examined the ability of multidimensional fluorescence spectroscopy and parallel factor analysis (PARAFAC) to provide detailed chemical information on the preferential sorption of higher-molecular-weight components of natural organic matter onto mineral surfaces. Dissolved organic matter (DOM) from soil organic horizons and tree leaf tissues was obtained using water extracts. The suite of fluorescence spectra was modeled with PARAFAC and it was revealed that the DOM extracts contained five fluorescing components: tryptophan-like (peak location at excitation <255 nm:emission 342 nm), tyrosine-like (276 nm:312 nm), and three humic-substance-like components (<255 nm:456 nm, 309 nm:426 nm, <255 nm:401 nm). In general, adsorption onto goethite and gibbsite increased with increasing DOM molecular weight and humification. PARAFAC analysis of the pre- and post-sorption DOM indicated that the ordering of sorption extent was humic-like components (average 91% sorption) > tryptophan-like components (52% sorption) > tyrosine-like components (29% sorption). This differential sorption of the modeled DOM components in both the soil organic horizon and leaf tissue extracts led to the fractionation of DOM. The results of this study demonstrate that multidimensional fluorescence spectroscopy combined with PARAFAC can quantitatively describe the chemical fractionation process due to the interaction of DOM with mineral surfaces. 相似文献