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121.
Podstawka E Ozaki Y Proniewicz LM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10807-10816
Raman (RS) and surface-enhanced Raman scattering spectra (SERS) were measured for various length carboxyl terminal fragments (X-14 of amino acid sequence) of bombesin ( BN): BN13-14, BN12-14, BN11-14, BN10-14, BN9-14, and BN8-14 in silver colloidal solutions. Density functional theory (DFT) calculations of Raman wavenumbers and intensities with extended basis sets (B3LYP/6-31++G**) were performed with the aim of providing the definitive band allocations to the normal coordinates. The proposed band assignment is consistent with the assignment for similar compounds reported in the literature. The nonadsorbed and adsorbed molecular structures were deducted by detailed spectral analysis of the RS and SERS spectra, respectively. This analysis also allowed us to propose the particular surface geometry and orientation of these peptides on silver surface, and their specific interaction with the surface. For example, a SERS spectrum of BN8-14 indicates that the interaction of a thioether atom and Trp8 with the silver surface is favorable and may dictate the orientation and conformation of adsorbed peptide. One of the most prominent and common features in all of the fragments' SERS spectra is a approximately 692 cm (-1) band due to nu(C-S) accompanied by two or three bands of different C-S conformers for all, except BN8-14, which suggests that all of the above-mentioned compounds adsorb on the silver surface through the thioether atom and that the attachment of Trp8 produces limitation in a number of possible C-S conformers adopted on this surface. Our results also show clearly that His12 and CO do not interact with the colloid surface, which supports our earlier results. 相似文献
122.
Niu J Liu Z Fu L Shi F Ma H Ozaki Y Zhang X 《Langmuir : the ACS journal of surfaces and colloids》2008,24(20):11988-11994
In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated. 相似文献
123.
Simon Burk Markus Albrecht Kazuhisa Hiratani 《Journal of inclusion phenomena and macrocyclic chemistry》2008,61(3-4):353-359
A novel tripodand-type ligand (L1) having three 2,3-dihydroxynaphthalene end groups and a C3 symmetric 1,3,5-tryimethylbenzene based backbone was prepared by the reaction of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with 3-(2-(hydroxymethyl)allyloxy)naphthalene-2-ol followed by triple Claisen rearrangement. A 1:1 titanium complex which acts as a metallo-cryptand is obtained by the reaction of ligand (L1) with Ti(IV)(=O)(acac)2 in the presence of base. The formation of the metallo-cryptand strongly depends on templating effects by counter cations and it shows a high selectively for the encapsulation of cesium cations in its cavity. 相似文献
124.
The idea of quality by design (QbD) has been proposed in pharmaceutical field. QbD is a systematic approach to control the product performance based on the scientific understanding of the product quality and its manufacturing process. In the present study, near-infrared (NIR) imaging is utilized as a tool to achieve this concept. A practical use of a chemometrics technique called self-modeling curve resolution (SMCR) is demonstrated with NIR imaging analysis of pharmaceutical tablets containing two ingredients, a soluble active ingredient, pentoxifylline (PTX), and an insoluble excipient, palmitic acid. Concentration profiles obtained by SMCR reveal that the homogenous distribution of chemical ingredients strongly depends on the grinding time and that its process plays a central role in quantitative control, say sustained-release of PTX. In addition, pure component spectra by SMCR indicate a sequential change of specific NIR peak intensities following the increase of the grinding time. The spectra change shows a molecular structure change related to its crystallinity during grinding process. Accordingly, this study clearly demonstrates that NIR imaging combined with SMCR can be a powerful tool to reveal chemical or physical mechanism induced by the manufacturing process of pharmaceutical products and that it may be a solid solution for QbD of pharmaceutical products. 相似文献
125.
Asymmetric Induction by a Nitrogen 14N/15N Isotopomer in Conjunction with Asymmetric Autocatalysis 下载免费PDF全文
Dr. Arimasa Matsumoto Hanae Ozaki Shunya Harada Kyohei Tada Tomohiro Ayugase Hitomi Ozawa Prof. Dr. Tsuneomi Kawasaki Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2016,55(49):15246-15249
Chirality arising from isotope substitution, especially with atoms heavier than the hydrogen isotopes, is usually not considered a source of chirality in a chemical reaction. An N2,N2,N3,N3‐tetramethyl‐2,3‐butanediamine containing nitrogen (14N/15N) isotope chirality was synthesized and it was revealed that this isotopically chiral diamine compound acts as a chiral initiator for asymmetric autocatalysis. 相似文献
126.
Shimizu H Fujimoto K Furusyo M Maeda H Nanai Y Mizuno K Inouye M 《The Journal of organic chemistry》2007,72(4):1530-1533
We newly prepared para- and meta-linked alkynylpyrene oligomers and examined their photophysical properties. Oligomerization of monomeric building blocks was performed by CuI-promoted oxidative coupling reaction. The resulting oligomers mainly consist of 2-mer to 6-mer that were assigned on the basis of MALDI-TOF mass spectra, and the 2-mer, 3-mer, and 4-mer were isolated and fully characterized. From their absorption and fluorescence spectra, the para-linked oligomers were found to be somewhat pi-conjugated compared with meta-linked ones, and the fluorescence quantum yields decreased with increasing oligomer length (Phif = 0.79-0.55). 相似文献
127.
A process of water sorption into a biocompatible polymer, poly(2-methoxyethyl acrylate) (PMEA), was investigated by time-resolved, in situ, attenuated total reflection infrared spectroscopy. Evidence for three different types of hydrated water in PMEA, that is, nonfreezing water, freezing bound water, and freezing water, were found. Each hydration structure was elucidated at the functional group level. Nonfreezing water, which never crystallizes, even at -100 degrees C, has a C=O...H-O type of hydrogen bonding interaction with the carbonyl group of PMEA. Freezing bound water, which crystallizes in a heating process below 0 degrees C, interacts with the methoxy moiety in the PMEA side chain terminal. Freezing water, which crystallizes approximately 0 degrees C, has bulk-water-like structure with an O-H...O-H hydrogen bonds network. It has been concluded from the present study that the methoxy moiety in the PMEA side chain terminal plays an important role for the excellent biocompatibility of PMEA. 相似文献
128.
S. -L. Guo L. Li H. -Y. Guo C. -Q. Tu Y. -L. Wang T. Doke T. Kato K. Ozaki A. Kyan Y. Piao T. Murakami 《Radiation measurements》1999,31(1-6):167-172
Bubble detectors which are commonly used as neutron detectors have been demonstrated through this study to be good detectors for registration of high energy heavy ion tracks. Large size bubble detectors made in China Institute of Atomic Energy were irradiated to heavy ions Ar and C up to 650 MeV/u and 400 MeV/u, respectively. Very clear features of stringy tracks of high energy heavy ions and their fragmentations are manifested and distinguishable. A single track created by a specific high energy heavy ion is composed of a line of bubbles, which is visible by naked eyes and retained for months wihhout reduction in size. The creation of heavy ion tracks in bubble detectors is governed by a threshold whose essence is approximately a critical value of energy loss rate (dE/dX)c similar to that of etch track detectors. Ranges of heavy ions in bubble detectors are apparent and predictable by existing formulas. Identification of high energy heavy ions and the applications to heavy ion physics, cosmic rays, exotic particles and cancer therapy monitoring are obviously promising. The experimental and theoretical aspects of high energy heavy ion tracks in bubble detectors as well as the expectable applications are presented and discussed. 相似文献
129.
Application of two-dimensional near-infrared correlation spectroscopy to protein research 总被引:6,自引:0,他引:6
The purpose of the present paper is to demonstrate the potential of generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in studies of hydration and structure of proteins. We describe here two examples. The first example is concerned with heat denaturation process of ovalbumin in aqueous solutions and the second one deals with isomerizations with varying pH of serum albumin. New insight has been obtained into the hydration and unfolding process of secondary structures of ovalbumin and serum albumin by studying temperature- or pH-dependent correlation patterns in 2D synchronous and asynchronous spectra. Generalized 2D NIR correlation spectroscopy emphasizes spectral features not readily observable in conventional one-dimensional spectra, enabling to extract subtle but valuable structural changes concerning with the protein denaturation. 相似文献
130.
It has been found that small mutations of certain genes are the definitive origin of many heritable disorders and cancers with striking development of recent molecular biology. Such new findings have taken close-up of the importance of gene mutation assays based on the difference of DNA base sequences in diagnostic or medical field Capillary electrophoresis can be a good candidate for an ideal method on such gene analysis, because the methods can be performed with trace amount of samples, high resolution and shorter running time. We have established an effect of oligonucleotide, which was introduced onto capillary inner surface, on the recognition of an overall sequence of sample DNA fragments as an affinity ligand. 相似文献