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101.
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103.
Abstract Derivatization, or chemical modification of analytes, is often required for species that are only weakly detectable by common spectroscopic methods. Derivatization is most commonly performed in homogeneous solution or using phase‐transfer catalyzed reactions. However, the use of solid phase supports for performing the same reactions has a number of advantages. The sample can be “cleaned up” on the same phase, eliminating interfering matrix components or excess reagent. The process naturally concentrates the analyte, providing higher sensitivity, but also, under favorable circumstances, provides for more efficient reactions relative to solutions of the same original concentration. This review explores the uses to which such supports have been put, primarily in fluorescence derivatization for chromatographic applications. Some of the considerations in applying these techniques are described, and they are shown to be an extremely useful format for derivatization. 相似文献
104.
Using carbodiimide reagents [1,3-diisopropylcarbodiimide or N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC)], we have developed a mild, generalized, one-pot method that delivers N-2-arylaminobenzimidazole esters from commercially available aryl isothiocyanates and o-phenylenediamines. Following saponification and acidifying, the benzimidazole acids were isolated in overall yields ranging from 75 to 88% from the starting aryl isothiocyanates. Nine benzimidazole acids were converted into a library consisting of 180 benzimidazole amides following EDC coupling with commercially available amines. The National Institute of General Medical Science will dispense these benzimidazole amides to academia groups for pilot scale biomedical studies. Using these mild conditions and environmentally safe reagents, we demonstrated that these pharmaceutically ornate heterocycles can also be constructed on solid support. 相似文献
105.
The reaction of vinyl radical with molecular oxygen in solid argon has been studied using matrix isolation infrared absorption spectroscopy. The vinyl radical was produced through high frequency discharge of ethylene. The vinyl radical reacted with oxygen spontaneously on annealing to form the vinylperoxy radical C(2)H(3)OO with the O-O bond in a trans position relative to the C-C bond, which is characterized by O-O stretching and out-of-plane CH(2) bending vibrations at 1140.7 and 875.5 cm(-1). The vinylperoxy radical underwent visible photon-induced dissociation to the CH(2)OH(CO) complex or CH(2)OH+CO, which has never been considered in previous studies. The CH(2)OH(CO) product was predicted to be more thermodynamically accessible than the previously reported major HCO+H(2)CO channel, and is most likely produced by hydrogen atom transfer from the first-formed H(2)CO-HCO pair in solid argon. 相似文献
106.
J.P. Seitz B.B. Back M.P. Carpenter I. Diszegi K. Eisenman P. Heckman D.J. Hofman M.P. Kelly T.L. Khoo S. Mitsuoka V. Nanal T. Pennington R.H. Siemssen M. Thoennessen R.L. Varner 《Nuclear Physics A》2005,750(2-4):245-255
The giant dipole resonance built on excited states was observed in very fissile nuclei in coincidence with evaporation residues. The reaction 48Ca + 176Yb populated evaporation residues of mass A=213–220 with a cross section of 200 μb at 259 MeV. The extracted giant dipole resonance parameters are in agreement with theoretical predictions for this mass region. 相似文献
107.
H. P. S. Chauhan Jaswant Carpenter Sumit Bhatiya Abhilasha Bakshi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1713-1722
Abstract Replacement reactions of bis(diethyldithiocarbamato)antimony(III) chloride have been carried out with oxygen and sulfur donor ligands such as disodium oxalate, sodium acetate, sodium salicylate, benzoic acid, thioglycolic acid, acetylacetone, thiphenol, ethane-1,2-dithiol, and 2,2-dimethylpropane-1,3-diol to give mixed bis(diethyldithiocarbamato)antimony(III) derivatives of the corresponding ligands. These derivatives have been characterized by the physicochemical [melting point and molecular weight determination, elemental analysis (C, H, N, S, and Sb)], spectral [FT-IR, far-IR, NMR (1H and 13C)], ESI-mass, powder XRD, and SEM studies. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables] 相似文献
108.
Ivan A. Popov Brennan S. Billow Stephanie H. Carpenter Enrique R. Batista James M. Boncella Aaron M. Tondreau Ping Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200114
A method to explore head-to-head ϕ back-bonding from uranium f-orbitals into allyl π* orbitals has been pursued. Anionic allyl groups were coordinated to uranium with tethered anilide ligands, then the products were investigated by using NMR spectroscopy, single-crystal XRD, and theoretical methods. The (allyl)silylanilide ligand, N-((dimethyl)prop-2-enylsilyl)-2,6-diisopropylaniline (LH), was used as either the fully protonated, singly deprotonated, or doubly deprotonated form, thereby highlighting the stability and versatility of the silylanilide motif. A free, neutral allyl group was observed in UI2(L1)2 ( 1 ), which was synthesized by using the mono-deprotonated ligand [K][N-((dimethyl)prop-2-enyl)silyl)-2,6-diisopropylanilide] (L1). The desired homoleptic sandwich complex U[L2]2 ( 2 ) was prepared from all three ligand precursors, but the most consistent results came from using the dipotassium salt of the doubly deprotonated ligand [K]2[N-((dimethyl)propenidesilyl)-2,6-diisopropylanilide] (L2). This allyl-based sandwich complex was studied by using theoretical techniques with supporting experimental spectroscopy to investigate the potential for phi (ϕ) back-bonding. The bonding between UIV and the allyl fragments is best described as ligand-to-metal electron donation from a two carbon fragment-localized electron density into empty f-orbitals. 相似文献
109.
Sang Bok Kim Robert D. Pike Prof. Jason S. D'Acchioli Prof. Brennan J. Walder Gene B. Carpenter Prof. Dwight A. Sweigart Prof. 《Angewandte Chemie (International ed. in English)》2009,48(10):1762-1765
Complex patterns : The arene manganese tricarbonyl complexes [Mn(η5‐2,5‐didodecoxy‐1,4‐semiquinone)(CO)3] and [Mn(η6‐1,4‐dioctyloxybenzene)(CO)3] BF4 form patterned monolayers on the surface of highly ordered pyrolytic graphite (HOPG), as a result of hydrogen‐bonding, hydrophobic, and electrostatic interactions, leading to an ordered 2D array of manganese atoms or ions.
110.
Gold nanoparticles appear to be superior handles in optical trapping assays. We demonstrate that relatively large gold particles (R(b)=50 nm) indeed yield a sixfold enhancement in trapping efficiency and detection sensitivity as compared to similar-sized polystyrene particles. However, optical absorption by gold at the most common trapping wavelength (1064 nm) induces dramatic heating (266 degrees C/W). We determined this heating by comparing trap stiffness from three different methods in conjunction with detailed modeling. Due to this heating, gold nanoparticles are not useful for temperature-sensitive optical-trapping experiments, but may serve as local molecular heaters. Also, such particles, with their increased detection sensitivity, make excellent probes for certain zero-force biophysical assays. 相似文献