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111.
The electronic spectrum of the nitridoosmate(VIII) ion, OsO3N-, has been measured at liquid helium temperatures for thin films of the n-tetrabutyl-ammonium salt and for oriented, doped LiClO4. 3H2O single crystals. Four structured band systems, all individually composed of superimposed A 1 ← A 1 and E←A 1 transitions, are observed at energies comparable to those of the two lowest 1 T 2←1 A 1 transitions of OsO4. Prominent vibronic structure assigned to ν(Os-N) is observed for all of the bands. The bands are assigned to transitions to completely spin-orbit mixed states. The highest filled orbitals of OsO3N- are oxygen-localized and π non-bonding. The nitrido ligand appears to ‘dominate’ the π-bonding in the ion. 相似文献
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Lisa M. Jones Hao Zhang Weidong Cui Sandeep Kumar Justin B. Sperry James A. Carroll Michael L. Gross 《Journal of the American Society for Mass Spectrometry》2013,24(6):835-845
As therapeutic monoclonal antibodies (mAbs) become a major focus in biotechnology and a source of the next-generation drugs, new analytical methods or combination methods are needed for monitoring changes in higher order structure and effects of post-translational modifications. The complexity of these molecules and their vulnerability to structural change provide a serious challenge. We describe here the use of complementary mass spectrometry methods that not only characterize mutant mAbs but also may provide a general framework for characterizing higher order structure of other protein therapeutics and biosimilars. To frame the challenge, we selected members of the IgG2 subclass that have distinct disulfide isomeric structures as a model to evaluate an overall approach that uses ion mobility, top-down MS sequencing, and protein footprinting in the form of fast photochemical oxidation of proteins (FPOP). These three methods are rapid, sensitive, respond to subtle changes in conformation of Cys?→?Ser mutants of an IgG2, each representing a single disulfide isoform, and may be used in series to probe higher order structure. The outcome suggests that this approach of using various methods in combination can assist the development and quality control of protein therapeutics. 相似文献
115.
Justin J. Maresh Sonia E. Chavez Matthew J. Asciutto Nathan D. Brown Alexander A. Delgado Youya Gao 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):683-688
Electrophilic trisubstituted ethylenes, phenoxy ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2CH3, where R is 4-(4-BrC6H5O), 2-(4-ClC6H5O), 3-(4-ClC6H5O), 4-(3-ClC6H5O), 4-(4-ClC6H5O), 4-(4-FC6H5O), 2-(3-CH3OC6H5O), 2-(4-CH3OC6H5O), 3-(4-CH3OC6H5O), 4-(4-CH3OC6H5O), 3-(4-CH3C6H5O) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of phenoxy ring-substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-(4-CH3OC6H5O) (6.07) > 3-(4-ClC6H5O) (3.38) > 3-(4-CH3OC6H5O) (2.78) > 4-(3-ClC6H5O) (2.77) > 2-(4-ClC6H5O) (2.29) > 3-(4-CH3C6H5O) (1.98) > 4-(4-FC6H5O) (1.92) > 4-(4-ClC6H5O) (1.89) > 2-(3-CH3OC6H5O) (1.39) > 2-(4-CH3OC6H5O) (0.90) > 4-(4-BrC6H5O) (0.77). Relatively high Tg of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (2.5-8.0% wt), which then decomposed in the 500-800°C range. 相似文献
116.
Dhirendra Kumar Dr. K. R. Justin Thomas Ching‐Chiao Lin Prof. Jwo‐Huei Jou 《化学:亚洲杂志》2013,8(9):2111-2124
A series of pyrenoimidazoles that contained various functional chromophores, such as anthracene, pyrene, triphenylamine, carbazole, and fluorene, were synthesized and characterized by optical, electrochemical, and theoretical studies. The absorption spectra of the dyes are dominated by electronic transitions that arise from the pyrenoimidazole core and the additional chromophore. All of the dyes exhibited blue‐light photoluminescence with moderate‐to‐high quantum efficiencies. They also displayed high thermal stability and their thermal‐decomposition temperatures fell within the range 462–512 °C; the highest decomposition temperature was recorded for a carbazole‐containing dye. The oxidation propensity of the dyes increased on the introduction of electron‐rich chromophores, such as triphenylamine or carbazole. The application of selected dyes that featured additional chromophores such as pyrene, carbazole, and triphenylamine as blue‐emissive dopants into multilayered organic light‐emitting diodes with a 4,4′‐bis(9H‐carbazol‐9‐yl)biphenyl (CBP) host was investigated. Devices that were based on triphenylamine‐ and carbazole‐containing dyes exhibited deep‐blue emission (CIE 0.157, 0.054 and 0.163, 0.041), whereas a device that was based on a pyrene‐containing dye showed a bright‐blue emission (CIE 0.156, 0.135). 相似文献
117.
Justin R. Denton 《合成通讯》2013,43(5):770-776
A protocol has been developed to purify 9-(trifluoroacetyl)anthracene from anthracene, the major impurity associated in its synthesis. The protocol utilizes a chemoselective thermal Diels–Alder reaction, employing maleic anhydride as the dienophile. The resulting Diels–Alder adduct can then be removed by extractive workup followed by recrystallization to give 9-(trifluoroacetyl)anthracene with ≥99% chemical purity. 相似文献
118.
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
119.
The conditions required for the accurate measurement of the sulfur content of cellulose nanocrystals (CNCs) by conductometric titration are discussed. CNCs from sulfuric acid hydrolysis are electrostatically stabilized in aqueous suspension due to the introduction of charged sulfate ester groups onto the surface of the crystallites during reaction. The sulfur content thus largely reflects the surface charge of the crystals, and is crucial to the characterization and understanding of material properties. Conductometric titration is commonly used to quantify the sulfur content of CNCs, however, the exhaustive removal of free acid by dialysis and the necessity, type, quantity and duration of ion-exchange resin treatments are not always consistent. Here we explore the standard conditions of dialysis, ion-exchange, and the reproducibility of titration results. Extensive dialysis is found to be effective in the removal of free acid, but similar results are also achieved in shorter times and with less water using membrane ultrafiltration. It is also shown that the conditions of ion-exchange most commonly employed in the literature can lead to inaccurate sulfur contents. Finally, good agreement is obtained between the sulfur contents of different CNC batches prepared using the same hydrolysis conditions, and from titration and elemental analysis when thoroughly purified, well-dispersed samples, and appropriate resin conditions are used. 相似文献
120.