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81.
Streeter I Wain AJ Thompson M Compton RG 《The journal of physical chemistry. B》2005,109(25):12636-12649
An in situ electrochemical electron spin resonance (ESR) study on the electro-oxidation of para-chloroaniline, para-bromoaniline, and para-iodoaniline dissolved in acetonitrile at gold electrodes is reported. ESR spectra obtained using a tubular flow cell reveal the presence of a paramagnetic dimer product derived from para-aminodiphenylamine, during oxidative electrolysis, suggesting the coupling of reactive electrogenerated radical cations with neutral parent haloaniline molecules. The ESR signal intensity behaves in a manner expected for a radical species reacting with second-order kinetics, suggesting the paramagnetic dimer is, itself, unstable. The theory describing the ESR signal intensity flow rate behavior for this reaction mechanism is developed for the tubular arrangement and used to extract mechanistic and kinetic data from the experimental results for the cases of para-chloroaniline and para-bromoaniline. Further mechanistic aspects, including proton and halide ion expulsion during dimerization, are explored voltammetrically and with the aid of digital simulations using Digisim. Comparison of the ESR signal and voltammetric measurements suggests that an additional mechanism operates which does not lead to paramagnetic products. Additionally, the in situ electrolysis of N,N-dimethyl-para-bromoaniline is reported to generate the stable radical cation of N,N,N',N'-tetramethylbenzidine, and a mechanism of electro-oxidation is, thus, proposed. 相似文献
82.
Wright RJ Phillips AD Hino S Power PP 《Journal of the American Chemical Society》2005,127(13):4794-4799
The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons. 相似文献
83.
John J. Monaghan Michael Barber Robert S. Bordoli R. Donald Sedgwick Andrew N. Tyler 《Journal of mass spectrometry : JMS》1983,18(2):75-82
Fast atom bombardment mass spectra of a range of involatile monophosphonated and mixed sulphonated/monophosphonated azo dyestuffs are presented. Good spectra are obtained and the fragmentations are discussed with special reference to the ions formed by cleavage of the azo linkage. The negative ion spectra are shown to be superior in terms of signal to background and structural information to those obtained in the positive ion mode. The results are compared with those obtained from sulphonated azo dyestuffs. 相似文献
84.
Venkatraman S Njoroge FG Girijavallabhan V McPhail AT 《The Journal of organic chemistry》2002,67(8):2686-2688
A novel synthesis of cis and trans substituted 4-tert-butoxycarbonyl cyclohexylglycines via asymmetric aminohydroxylation of vinyl styrene followed by reduction of the aromatic ring and subsequent oxidation is reported. 相似文献
85.
Gunnlaugsson T Leonard JP Sénéchal K Harte AJ 《Chemical communications (Cambridge, England)》2004,(7):782-783
The cationic cyclen based Eu(III)-phen conjugated 1.Eu was synthesised as a chemosensor for Cu(II), where the recognition in water at pH 7.4 gave rise to quenching of the Eu(III) luminescence and the formation of tetranuclear polymetallic Cu(II)-Eu(III) macrocyclic complexes in solution where Cu(II) was bound by three 1.Eu conjugates. 相似文献
86.
A reagent panel comprised of seven aryl beta-D-N-acetylneuraminides was synthesized and then used to probe the mechanisms of nonenzymatic hydrolysis. These reactions proceeded via four independent pathways: (1) acid-catalyzed hydrolysis of the neutral molecule; (2) acid-catalyzed hydrolysis of the anionic form, or its kinetic equivalent spontaneous hydrolysis of the neutral form; (3) spontaneous hydrolysis of the anionic form; and (4) a base-promoted pathway. The pH-independent spontaneous hydrolysis of 4-nitrophenyl alpha-D-N-acetylneuraminide (5) occurs at a rate that is over 100 times faster than that of the corresponding reaction of 4-nitrophenyl beta-D-N-acetylneuraminide (4a). Spontaneous hydrolyses of four aryl beta-D-N-acetylneuraminides displayed a beta(lg) value of -1.24 +/- 0.16 (pH = 8.1, T = 100 degrees C), and at a pH value of 1.0 (50 degrees C), all seven panel members gave a beta(lg) value of 0.14 +/- 0.08. The aqueous ethanolyses of 4a and 5 gave similar products and displayed sensitivity parameters (m) in a standard Winstein-Grunwald analysis of -0.04 +/- 0.01 and +0.23 +/- 0.02, respectively. These results, plus the activation parameters calculated for the spontaneous hydrolyses of the anionic forms of 5 (DeltaH() = 116 +/- 2 kJ mol(-1) and DeltaS = 27 +/- 4 J mol(-1) K(-1)) and 4a (DeltaH = 138 +/- 3 kJ mol(-1) and DeltaS = 59 +/- 8 J mol(-1) K(-1)), are inconsistent with anomeric carboxylate assistance occurring during the hydrolysis reactions, and the likely cause for the enhanced reactivity of 5 in comparison to that of 4a is an increase in ground-state steric strain. 相似文献
87.
Bond AD Derossi S Jensen F Larsen FB McKenzie CJ Nelson J 《Inorganic chemistry》2005,44(17):5987-5989
Treatment of cryptand L(1) with Cu(II) generates a H3O2(-)-bridged dicopper(II) cryptate, 2, where the guest anion has responded to steric constraint by a significant shortening of the O-O distance to 2.325(9) A; computational optimization at the B3LYP/6-31(d) level suggests that the bridging O-H...O H-bond is bent (approximately 157 degrees) but that the barrier to interchange of the bridging H atom is low (<4 kJ mol(-1)). This cryptate, rather than the [Cu2L(1)muCN]3+ species recently claimed to derive from cleavage of the C-C bond of the solvent, is the product of acetonitrile recrystallization of the initially formed reaction product, 1. 相似文献
88.
Yuko Ogata Pamela M. Quizon Nancy S. Nightlinger Pongkwan Sitasuwan Casey Snodgrass L. Andrew Lee Jeffrey D. Meyer Richard S. Rogers 《Rapid communications in mass spectrometry : RCM》2022,36(3):e9222
Rationale
The multi-attribute method (MAM) has become a valuable mass spectrometry (MS)-based tool that can identify and quantify the site-specific product attributes and purity information for biotherapeutics such as monoclonal antibodies (mAbs) and fusion molecules in recent years. As we expand the use of the MAM at various stages of drug development, it is critical to enhance the sample preparation throughput without additional chemical modifications and variability.Methods
In this study, a fully automated MAM sample preparation protocol is presented, where rapid desalting in less than 15 minutes is achieved using miniaturized size-exclusion chromatography columns in pipette tips on an automated liquid handler. The peptide samples were analyzed using an electrospray ionization (ESI) orbitrap mass spectrometer coupled to an ultra-high-performance liquid chromatography (UHPLC) system with a dual column switching system.Results
No significant change was observed in product attributes and their quantities compared with manual, low-artifact sample preparation. The sample recovery using the buffer exchange tips was greatly enhanced over the manual spin cartridges while still demonstrating excellent reproducibility for a wide variety of starting sample concentrations. Unlike a plate desalting system, the individual columns provide flexibility in the number of samples prepared at a time and sample locations within plates.Conclusions
This automated protocol enables the preparation of up to 96 samples with less “at-bench” time than the manual preparation of a smaller batch of samples, thereby greatly facilitating support of process development and the use of the MAM in quality control.89.
The product from the fluorination of pyridine by KCoF4 at ca. 220° contains eleven fluoropyridines, two fluoro-2-azahex-enes, three azahexa- dienes, and two fluoro-N-methylpyrrolidines, besides an azacyclohexa-1,3- diene. Four products were isolated from a fluorination of pyridine by CoF3 at ca. 150°, a 2-azahexene, two N-methylpyrrolidines, and 4H-nona- fluoropiperidine. 相似文献
90.
Ulrike Troitzsch Andrew G. Christy David J. Ellis 《Journal of solid state chemistry》2007,180(10):2885-2895
We report a new zirconium titanate compound (Zr,Ti)O2 with 27.5-35 mol% titania (TiO2) formed from the oxides at 35-38 kbar, 1400-1500 °C. Crystal structure investigations at atmospheric conditions with powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed a monoclinic structure related to that of M-fergusonite (beta). Unit-cell dimensions (from 27.5 to 35 mol% TiO2): a=7.267(20)-7.340(2) Å, b=10.435(3)-10.429(1) Å, c=5.023(11)-5.040(1) Å, β=136.45(12)-137.55(1)°, V=262.44(92)-260.40(12) Å3, Z=4. Rietveld refinement (RF=1.55) of a sample with 32.8 mol% TiO2 indicates that site A is 8-fold coordinated, mostly occupied by Zr, while site B has 6-fold average coordination, occupied by Ti and Zr. Site B is at least partly ordered, as indicated by superstructure reflections 0 0 1 and −2 0 1 detected with TEM, reducing the space group from C2/c to C2. Pronounced streaking of selected diffraction spots is linked to the boundaries of lamellar domains in twin orientation, with twin planes either (200) or (20−2). Adjacent lamellae differ slightly in composition, causing subtle asymmetry of the twin diffraction patterns. 相似文献