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51.
Prof. Kengo Hanaya Kaho Yamoto Prof. Kazuaki Taguchi Prof. Kazuaki Matsumoto Prof. Shuhei Higashibayashi Prof. Takeshi Sugai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201677
The chemical modification of proteins is an effective technique for manipulating the properties and functions of proteins, and for creating protein-based materials. The N-terminus is a promising target for single-site modification that provides modified proteins with uniform structures and properties. In this paper, a copper(II)-mediated aldol reaction with 2-pyridinecarboxaldehyde (2-PC) derivatives is proposed as an operationally simple method to selectively modify the N-terminus of peptides and proteins at room temperature and physiological pH. The copper(II) ion activates the N-terminal amino acids by complexation with an imine of the N-terminal amino acid and 2-PCs, realizing the selective formation of the nucleophilic intermediate at the N-terminus. This results in a stable carbon-carbon bond between the 2-PCs and the α-carbon of various N-terminal amino acids. The reaction is applied to four different proteins, including biopharmaceuticals such as filgrastim and trastuzumab. The modified trastuzumab retains the human epidermal growth factor receptor 2 recognition activity. 相似文献
52.
Abstract The polymerizations of alkyl esters of propiolic acid by Rh complex catalysts were investigated. [Rh(norbornadiene)Cl]2, which was the most active among the catalysts examined, gave rise to poly(alkyl propiolate) in a fairly high yield (~80%) in the presence of alcohol as the polymerization solvent. The polymers formed were a pale yellow powder soluble in common organic solvents except for poly(methyl propiolate). The structures of the polymers obtained were investigated by IR, 13C-NMR, CP MAS 13C-NMR, and laser Raman spectroscopies, together with the x-ray diffraction method. Based on these spectroscopic data, it was concluded that this Rh complex can be called a stereoregular polymerization catalyst of alkyl propiolate because the poly(alkyl propiolate) obtained has a cis-transoidal structure. 相似文献
53.
Polymerizations of cyclooctene, 5-methyl, 5-chloro-, and 5-methoxycyclooctenes were studied. Cyclooctene (CO) and 5-methylcyclooctene (MCO) provided high polymers in 80% yield with the use of WCl6/AlEti.B Clu5 or WCl6/AlEtCl2 catalyst. 5-Chlorocyclooctene gave oligomer in 50% yield with WCl6/AlEt2Cl catalyst. Neither polymer nor oligomer was produced from 5-methoxycyclooctene. These polymers were found to be produced through a ring-opening mechanism. The ratio of cis to trans structure in poly(CO) and poly(MCO) was determined by measurements of the decoupled ′H-NMR spectrum. Poly(CO) containing more than 50% trans structure was a crystalline solid at room temperature, while the polymer containing 30% of trans structure did not crystallize at room temperature. Poly(MCO) was amorphous, regardless of the content of trans structure. Poly(CO) and poly(MCO) obtained with MoCU/AlEtaCl or MoCU/AlEtCb catalyst contained no carbon-carbon double bond, and a vinyl polymerization mechanism was expected for this system. 相似文献
54.
Toyoji Kakuchi Toshifumi Satoh Junji Mata Satoshi Umeda Hisaho Hashimoto Kazuaki Yokota 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):325-336
Abstract The cyclopolymerizations of 1,2:5,6-dianhydro-3,4-di-O-pentyl-D-mannitol (1b) and 1,2:5,6-dianhydro-3,4-di-O-decyl-D-mannitol (1c) were carried out using BF3OEt2 and t-BuOK. All the resulting polymers consisted of cyclic constitutional units, i.e., the extent of cyclization was 100%. The polymer structures for the polymerization with t-BuOK were (1→6)-2,5-anhydro-3,4-di-O-pentyl-D-glucitol (2b) and (1→6)-2,5-anhydro-3,4-di-O-decyl-D-glucitol (2c), whereas those with BF3O-decyl2 comprised 2,5-anhydro-D-glucitols as major units along with other cyclic ones. These polymers were soluble in n-hexane, CHCl3, and THF, but insoluble in water, which differs from the amphiphilic solubility of (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitol (2a). The cation-binding properties of 2b and 2c were examined using alkali-metal picrates in order to compare them with those of 2a. The extraction yields for each cation decreased in the order of 2c < 2b < 2a. Every polymer exhibited a similar cation-binding selectivity in the order Cs+ > Rb+ > K+ ? Na+ > Li+. The ratio of K+ and Na+, K+/Na+, was 4.6 for 2a, 5.1 for 2b, and 7.1 for 2c in the increasing order 2a < 2b > 2c. 相似文献
55.
56.
Masahiro Yodoshi Natsumi Ikeda Naoko Yamaguchi Mana Nagata Noriaki Nishida Kazuaki Kakehi Takao Hayakawa Shigeo Suzuki 《Electrophoresis》2013,34(22-23):3198-3205
We have identified novel CE conditions for the separation of 7‐amino‐4‐methylcoumarin‐labeled monosaccharides and oligosaccharides from glycoproteins. Using a neutrally coated capillary and alkaline borate buffer containing hydroxypropylcellulose and ACN, saccharide derivatives form anionic borate complexes, which move from the cathode to the anode in an electric field and are detected near the anodic end. Excess labeling reagents and other fluorescent products remain at the cathodic end. Fluorimetric detection using an LED as a light source enables determination of monosaccharide derivatives with good linearity between at least 0.4 and 400 μM, may correspond to 140 amol to 140 fmol. The lower LOD (S/N = 5) is only 80 nM in the sample solution (ca. 28 amol). The results were comparable to reported values using fluorometric detection LC. The method was also applied to the analysis of oligosaccharides that were enzymatically released from glycoproteins. Fine resolution enables profiling of glycans in glycoproteins. The applicability of the method was examined by applying it to other derivatives labeled with nonacidic tags such as ethyl p‐aminobenzoate‐ and 2‐aminoacridone‐labeled saccharides. 相似文献
57.
The anomalous temperature dependence of the sign of the spontaneous polarization in a biphenyl ester series of ferroelectric liquid crystals is reported. The reversal of the sign of the spontaneous polarization in the chiral smectic C phase of 2MBNCBC ((S)-2′-methylbutyl-4′-n- nonylcarbonyloxy-(l,l′-biphenyl)-l-carboxylate) is observed at T m. This anomaly is studied in detail as functions of the length of the terminal alkyl chain, the applied electric field, the frequency and the applied hydrostatic pressure. T m has been confirmed to depend on the length of the terminal chain and the applied pressure. However, it is independent of the applied field and the measuring frequency. In the mixture of these compounds, this anomaly is also observed. 相似文献
58.
Masahide Tominaga Hiroyuki Ukai Kosuke Katagiri Kazuaki Ohara Kentaro Yamaguchi Isao Azumaya 《Tetrahedron》2014
Five macrocyclic molecules (1–5) were efficiently synthesized from the dimerization and trimerization of di-substituted adamantane derivatives, which were composed of three different aromatic units and two different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with channels that assembled into three-dimensional networks through CH/π interactions. 相似文献
59.
Kazuaki Z. Takahashi 《Journal of computational chemistry》2014,35(11):865-875
In our previous study (Takahashi et al., J. Chem. Theory Comput. 2012, 8, 4503), we developed the linear‐combination‐based isotropic periodic sum (LIPS) method. The LIPS method is based on the extended isotropic periodic sum theory that produces a ubiquitous interaction potential function to estimate homogeneous and heterogeneous systems. The LIPS theory also provides the procedure to design a periodic reaction field. To demonstrate this, in the present work, a novel reaction field of the LIPS method was developed. The novel reaction field was labeled LIPS‐SW, because it provides an interaction potential function with a shape that resembles that of the switch function method. To evaluate the ability of the LIPS‐SW method to describe in homogeneous and heterogeneous systems, we carried out molecular dynamics (MD) simulations of bulk water and water–vapor interfacial systems using the LIPS‐SW method. The results of these simulations show that the LIPS‐SW method gives higher accuracy than the conventional interaction potential function of the LIPS method. The accuracy of simulating water–vapor interfacial systems was greatly improved, while that of bulk water systems was maintained using the LIPS‐SW method. We conclude that the LIPS‐SW method shows great potential for high‐accuracy, high‐performance computing to allow large scale MD simulations. © 2014 Wiley Periodicals, Inc. 相似文献
60.
Dr. Jeffery M. Tharp Dr. Omer Ad Dr. Kazuaki Amikura Fred R. Ward Emma M. Garcia Prof. Dr. Jamie H. D. Cate Prof. Dr. Alanna Schepartz Prof. Dr. Dieter Söll 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3146-3150
By transplanting identity elements into E. coli tRNAfMet, we have engineered an orthogonal initiator tRNA (itRNATy2) that is a substrate for Methanocaldococcus jannaschii TyrRS. We demonstrate that itRNATy2 can initiate translation in vivo with aromatic non-canonical amino acids (ncAAs) bearing diverse sidechains. Although the initial system suffered from low yields, deleting redundant copies of tRNAfMet from the genome afforded an E. coli strain in which the efficiency of non-canonical initiation equals elongation. With this improved system we produced a protein containing two distinct ncAAs at the first and second positions, an initial step towards producing completely unnatural polypeptides in vivo. This work provides a valuable tool to synthetic biology and demonstrates remarkable versatility of the E. coli translational machinery for initiation with ncAAs in vivo. 相似文献