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91.
Carola W. N. Damen Weibin Chen Asish B. Chakraborty Mike van Oosterhout Jeffrey R. Mazzeo John C. Gebler Jan H. M. Schellens Hilde Rosing Jos H. Beijnen 《Journal of the American Society for Mass Spectrometry》2009,20(11):2021-2033
Monoclonal antibodies are typically glycosylated at asparagine residues in the Fc domain, and glycosylation heterogeneity
at the Fc sites is well known. This paper presents a method for rapid analysis of glycosylation profile of the therapeutic
monoclonal antibody trastuzumab from different production batches using electrospray quadrupole ion-mobility time-of-flight
mass spectrometry (ESI-Q-IM-TOF). The global glycosylation profile for each production batch was obtained by a fast LC-MS
analysis, and comparisons of the glycoprofiles of trastuzumab from different lots were made based on the deconvoluted intact
mass spectra. Furthermore, the heterogeneity at each glycosylation site was characterized at the reduced antibody level and
at the isolated glycopeptide level. The glycosylation site and glycan structures were confirmed by performing a time-aligned-parallel
fragmentation approach using the unique dual-collision cell design of the instrument and the incorporated ion-mobility separation
function. Four different production batches of trastuzumab were analyzed and compared in terms of global glycosylation profiles
as well as the heterogeneity at each glycosylation site. The results show that each batch of trastuzumab shares the same types
of glycoforms but relative abundance of each glycoforms is varied. 相似文献
92.
Fackler P Berthold C Voss F Bach T 《Journal of the American Chemical Society》2010,132(45):15911-15913
A chiral epoxidation catalyst based on a tricyclic octahydro-1H-4,7-methanoisoindol-1-one scaffold, in which a hydrogen bonding site and the catalytically active ruthenium center are spatially separated, was synthesized. It was shown that epoxidation reactions in such a supramolecular catalyst occur with high enantio- and regioselectivity because the hydrogen bonds expose the substrate to the ruthenium porphyrin complex with a clear conformational preference. The epoxidation of 3-vinylquinolone proceeded in up to 95% ee (71% yield). 相似文献
93.
A Mukherjee TK Sen PK Ghorai PP Samuel C Schulzke SK Mandal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10530-10545
Herein, we report the synthesis and characterization of two organozinc complexes that contain symmetrical phenalenyl (PLY)-based N,N-ligands. The reactions of phenalenyl-based ligands with ZnMe(2) led to the formation of organozinc complexes [N(Me),N(Me)-PLY]ZnMe (1) and [N(iPr),N(iPr)-PLY]ZnMe (2) under the evolution of methane. Both complexes (1 and 2) were characterized by NMR spectroscopy and elemental analysis. The solid-state structures of complexes 1 and 2 were determined by single-crystal X-ray crystallography. Complexes 1 and 2 were used as catalysts for the intramolecular hydroamination of unactivated primary and secondary aminoalkenes. A combined approach of NMR spectroscopy and DFT calculations was utilized to obtain better insight into the mechanistic features of the zinc-catalyzed hydroamination reactions. The progress of the catalysis for primary and secondary aminoalkene substrates with catalyst 2 was investigated by detailed kinetic studies, including kinetic isotope effect measurements. These results suggested pseudo-first-order kinetics for both primary and secondary aminoalkene activation processes. Eyring and Arrhenius analyses for the cyclization of a model secondary aminoalkene substrate afforded ΔH(≠) =11.3?kcal?mol(-1) , ΔS(≠) =-35.75?cal?K(-1) mol(-1) , and E(a) =11.68?kcal?mol(-1) . Complex 2 exhibited much-higher catalytic activity than complex 1 under identical reaction conditions. The in situ NMR experiments supported the formation of a catalytically active zinc cation and the DFT calculations showed that more active catalyst 2 generated a more stable cation. The stability of the catalytically active zinc cation was further supported by an in situ recycling procedure, thereby confirming the retention of catalytic activity of compound 2 for successive catalytic cycles. The DFT calculations showed that the preferred pathway for the zinc-catalyzed hydroamination reactions is alkene activation rather than the alternative amine-activation pathway. A detailed investigation with DFT methods emphasized that the remarkably higher catalytic efficiency of catalyst 2 originated from its superior stability and the facile formation of its cation compared to that derived from catalyst 1. 相似文献
94.
This contribution focuses on a novel phase-field model for a high-order phase-field approach to brittle fracture in the range finite deformation. In particular, two different challenges are tackled in this study: First, we want to establish a polyconvex free energy density to ensure the existence of a minimizer for the coupled problem, second, we have to deal with a fourth-order Cahn-Hilliard type equation for the approximation of the phase-field. Phase-field methods employ a variational framework for brittle fracture and have proven to predict complex fracture patterns in two and three dimensional examples. Basis of the model are the conjugate stresses of the three strain measures deformation gradient (line map), its cofactor (area map) and its determinant (volume map). The introduction of the tensor cross product simplifies the presentation of the first Piola-Kirchhoff stress tensor and its derivatives in elegant manner. The proposed Cahn-Hilliard type equation requires global -continuity. Therefore, we apply an isogeometric framework using NURBS basis functions. Moreover, a general hierarchical refinement scheme based on subdivision projection is used here for one, two and three dimensional simulations. This technique allows to enhance the approximation space using finer splines on each level but preserves the partition of unity as well as the continuity properties of the original discretization. We finally demonstrate the accuracy and the robustness with a series of benchmark problems. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
95.
Avijit Maiti Jessica Stubbe Nicols I. Neuman Pankaj Kalita Prakash Duari Carola Schulzke Vadapalli Chandrasekhar Biprajit Sarkar Anukul Jana 《Angewandte Chemie (International ed. in English)》2020,59(17):6729-6734
Diradicals have been of tremendous interest for over a century ever since the first reports of p‐ and m‐phenylene‐bridged diphenylmethylradicals in 1904 by Thiele and 1915 by Schlenk. Reported here are the first examples of cyclic(alkyl)(amino)carbene (CAAC) analogues of Thiele's hydrocarbon, a Kekulé diradical, and Schlenk's hydrocarbon, a non‐Kekulé diradical, without using CAAC as a precursor. The CAAC analogue of Thiele's hydrocarbon has a singlet ground state, whereas the CAAC analogue of Schlenk's hydrocarbon contains two unpaired electrons. The latter forms a dimer, by an intermolecular double head‐to‐tail dimerization. This straightforward synthetic methodology is modular and can be extended for the generation of redox‐active organic compounds. 相似文献
96.
Helmut Alt Alon Efrat Günter Rote Carola Wenk 《Journal of Algorithms in Cognition, Informatics and Logic》2003,49(2):262-283
The subject of this paper are algorithms for measuring the similarity of patterns of line segments in the plane, a standard problem in, e.g., computer vision, geographic information systems, etc. More precisely, we define feasible distance measures that reflect how close a given pattern H is to some part of a larger pattern G. These distance measures are generalizations of the well-known Fréchet distance for curves. We first give an efficient algorithm for the case that H is a polygonal curve and G is a geometric graph. Then, slightly relaxing the definition of distance measure, we give an algorithm for the general case where both, H and G, are geometric graphs. 相似文献
97.
In dendrochronology wood samples are dated according to the tree rings they contain. The dating process consists of comparing the sequence of tree ring widths in the sample to a dated master sequence. Assuming that a tree forms exactly one ring per year a simple sliding algorithm solves this matching task.
But sometimes a tree produces no ring or even two rings in a year. If a sample sequence contains this kind of inconsistencies it cannot be dated correctly by the simple sliding algorithm. We therefore introduce a algorithm for dating such a sample sequence against an error-free master sequence, where n and m are the lengths of the sequences. Our algorithm takes into account that the sample might contain up to missing or double rings and suggests possible positions for these kind of inconsistencies. This is done by employing an edit distance as the distance measure. 相似文献
98.
Broderick EM Guo N Wu T Vogel CS Xu C Sutter J Miller JT Meyer K Cantat T Diaconescu PL 《Chemical communications (Cambridge, England)》2011,47(35):9897-9899
The activity of cerium alkoxide complexes supported by a Schiff base ligand was controlled using redox reagents during the ring-opening polymerization of L-lactide. The rate of L-lactide polymerization was modified by switching in situ between the cerium(III) and cerium(IV) species. 相似文献
99.
Scepaniak JJ Harris TD Vogel CS Sutter J Meyer K Smith JM 《Journal of the American Chemical Society》2011,133(11):3824-3827
The four-coordinate iron(II) phosphoraniminato complex PhB(MesIm)(3)Fe-N═PPh(3) undergoes an S = 0 to S = 2 spin transition with T(C) = 81 K, as determined by variable-temperature magnetic measurements and Mo?ssbauer spectroscopy. Variable-temperature single-crystal X-ray diffraction revealed that the S = 0 to S = 2 transition is associated with an increase in the Fe-C and Fe-N bond distances and a decrease in the N-P bond distance. These structural changes have been interpreted in terms of electronic structure theory. 相似文献
100.
Broderick EM Guo N Vogel CS Xu C Sutter J Miller JT Meyer K Mehrkhodavandi P Diaconescu PL 《Journal of the American Chemical Society》2011,133(24):9278-9281
The activity of an yttrium alkoxide complex supported by a ferrocene-based ligand was controlled using redox reagents during the ring-opening polymerization of L-lactide. The oxidized complex was characterized by X-ray crystallography and (1)H NMR, XANES, and M?ssbauer spectroscopy. Switching in situ between the oxidized and reduced yttrium complexes resulted in a change in the rate of polymerization of L-lactide. Synthesized polymers were analyzed by gel permeation chromatography. Polymerization of trimethylene carbonate was also performed with the reduced and oxidized forms of an indium alkoxide complex. The indium system showed the opposite behavior to that of yttrium, revealing a metal-based dependency on the rate of polymerization. 相似文献