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排序方式: 共有238条查询结果,搜索用时 15 毫秒
1.
Summary The acid-catalysed decarboxylation of thecis-- andcis--[CoL(CO3)]+ complexes (L = 3,6-dimethyl-1,8-diamino-3,6-diazaoctane) have been studied over a range of HClO4 concentrations and the temperatures 25, 35 and 45° at I = 1.0 mol dm–3 (NaClO4). The rate expression takes the form kobs = k0 + k1[H+] where kobs is the observed first order rate constant at constant hydrogen ion concentration. The k0 term makes only a minor contribution to the overall reaction. Both complexes display solvent deuterium isotope effects ofca. 2.6 for the acid-catalysed decarboxylation, consistent with a rapid proton pre-equilibrium mechanism. Activation parameters have been determined and the mechanism of the reaction discussed. The magnitude of the solvent isotope effect is consistent with an A-1 type mechanism involving formation of a 5-coordinate intermediate. 相似文献
2.
In the work described here, a biosensor was developed for the determination of sulfite in food. Malva vulgaris tissue homogenate containing sulfite oxidase enzyme was used as the biological material. M. vulgaris tissue homogenate was crosslinked with gelatin using glutaraldehyde and fixed on a pretreated Teflon membrane. Sulfite was enzymatically converted to sulfate in the presence of the dissolved oxygen, which was monitored amperometrically. Sulfite determination was carried out by standard curves, which were obtained by the measurement of consumed oxygen level related to sulfite concentration. Several operational parameters had been investigated: the amounts of plant tissue homogenate and gelatin, percentage of glutaraldehyde, optimum pH and temperature. Also, some characterization studies were done. There was linearity in the range between 0.2 and 1.8 mM at 35 °C and pH 7.5. The results of real sample analysis obtained with the biosensor agreed well with the enzymatic reference method using spectrophotometric detection. 相似文献
3.
M. A. Bakir T. Yaseen A. Sarheel I. Othman 《Journal of Radioanalytical and Nuclear Chemistry》2004,260(3):607-612
The aim of this study was to investigate the relationship of selenium concentration in blood components and tumour tissues
of breast cancer patients and healthy volunteers (control), in Syria, using instrumental neutron activation analysis (INAA).
Red blood cells and serum selenium concentrations were determined in 50 healthy volunteers aged 25-70 years and 70 breast
cancer patients aged 25-84 years. Selenium levels were also measured in malignant and adjacent normal tissues from breast
cancer patients. The accuracy of the analysis was evaluated by co-analyses of international reference materials. The results
showed that selenium concentration in serum and RBC was significantly lower among breast cancer patients compared to healthy
volunteers (P<0.001). The results also showed that the selenium concentration was significantly higher in the cancer tissues compared to
adjacent normal tissues (P<0.001). We conclude that there is a good indication for selenium deviation in blood and malignant tissue of breast cancer
patients compared to that of healthy volunteers.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
4.
Kanda S. Ramasamy Farid Bakir Brenda Baker P. Dan Cook 《Journal of heterocyclic chemistry》1993,30(5):1373-1377
The synthesis of benzylated N2-(4,7,10,13-tetraazatridec-1-yl)-2′-deoxyguanosines 4 was accomplished by a key nucleophilic reaction of the novel unsymmetrical polyamine 2 , with 3′,5′-O-(tetraisopropyldisiloxane-1,3-diyl)-2-chloro-2′-deoxyinosine ( 1 ). 相似文献
5.
Yixuan Xie Siyu Chen Qiongyu Li Ying Sheng Michael Russelle Alvarez Joeriggo Reyes Gege Xu Kemal Solakyildirim Carlito B. Lebrilla 《Chemical science》2021,12(25):8767
A cross-linking method is developed to elucidate glycan-mediated interactions between membrane proteins through sialic acids. The method provides information on previously unknown extensive glycomic interactions on cell membranes. The vast majority of membrane proteins are glycosylated with complicated glycan structures attached to the polypeptide backbone. Glycan–protein interactions are fundamental elements in many cellular events. Although significant advances have been made to identify protein–protein interactions in living cells, only modest advances have been made on glycan–protein interactions. Mechanistic elucidation of glycan–protein interactions has thus far remained elusive. Therefore, we developed a cross-linking mass spectrometry (XL-MS) workflow to directly identify glycan–protein interactions on the cell membrane using liquid chromatography-mass spectrometry (LC-MS). This method involved incorporating azido groups on cell surface glycans through biosynthetic pathways, followed by treatment of cell cultures with a synthesized reagent, N-hydroxysuccinimide (NHS)–cyclooctyne, which allowed the cross-linking of the sialic acid azides on glycans with primary amines on polypeptide backbones. The coupled peptide–glycan–peptide pairs after cross-linking were identified using the latest techniques in glycoproteomic and glycomic analyses and bioinformatics software. With this approach, information on the site of glycosylation, the glycoform, the source protein, and the target protein of the cross-linked pair were obtained. Glycoprotein–protein interactions involving unique glycoforms on the PNT2 cell surface were identified using the optimized and validated method. We built the GPX network of the PNT2 cell line and further investigated the biological roles of different glycan structures within protein complexes. Furthermore, we were able to build glycoprotein–protein complex models for previously unexplored interactions. The method will advance our future understanding of the roles of glycans in protein complexes on the cell surface.The cell surface glycocalyx is highly interactive defined by extensive covalent and non-covalent interactions. A method for cross-linking and characterizing glycan–peptide interactions in situ is developed. 相似文献
6.
Alya A. Dawood Martin C. Grossel Robert M. Richardson Bakir A. Timimi Neil J. Wells 《Liquid crystals》2017,44(1):106-126
ABSTRACTOne of the current challenges in liquid crystal science is to understand the molecular factors leading to the formation of the intriguing twist-bend nematic phase (NTB) and determine its properties. During our earlier hunt for the NTB phase created on cooling directly from the isotropic phase and not the nematic phase, we had prepared 30 symmetric liquid crystal dimers. These had odd spacers and methylene links to the two mesogenic groups; desirable but clearly not essential features for the formation of the NTB. Here, we report the phases that the dimers exhibit and their transition temperatures as functions of both the lengths of the spacer and the terminal chains. In addition we describe the transitional entropies, their optical textures, the X-ray scattering patterns and the 2H NMR spectra employed in characterising the phases. All of which may lead to important properties of the twist-bend nematic phase. 相似文献
7.
8.
Theoretical investigation on hydrazine (N2H4) adsorption on Ni(111) was done by using density functional theory. Stability and mechanism of hydrazine adsorption in anti, gauche and cis conformation on nickel surface were studied. Charge transfer between lone-pair orbital and d-band was found to stabilize the anti-conformation as the most stable conformation, in contrast with hydrazine in the gas-phase where gauche conformation is more favored. However, the derived anti-bonding state between adsorbate and substrate is partially occupied due to the spin-polarization in the local states near the Fermi level and thus contributes in weakening the bonding. The stable adsorption structure was further verified by comparing the calculated vibrational frequencies with HREELS measurement results. The results were found to be in agreement with experimental results. It was also found that the adsorption in cis-conformation is a transition state as evident from the existence of imaginary frequency on its lowest vibrational mode which belongs to NH2 torsional movement around N–N axis. 相似文献
9.
Ayse Z. Aroguz Kemal Baysal Zelal Adiguzel Bahattin M. Baysal 《Applied biochemistry and biotechnology》2014,173(2):433-448
Hydrogels are attractive biomaterials for three-dimensional cell culture and tissue engineering applications. The preparation of hydrogels using alginate and gelatin provides cross-linked hydrophilic polymers that can swell but do not dissolve in water. In this work, we first reinforced pure alginate by using polyoxyethylene as a supporting material. In an alginate/PEO sample that contains 20 % polyoxyethylene, we obtained a stable hydrogel for cell culture experiments. We also prepared a stable alginate/gelatin hydrogel by cross-linking a periodate-oxidized alginate with another functional component such as gelatin. The hydrogels were found to have a high fluid uptake. In this work, preparation, characterization, swelling, and surface properties of these scaffold materials were described. Lyophilized scaffolds obtained from hydrogels were used for cell viability experiments, and the results were presented in detail. 相似文献
10.
The next-nearest-neighbour (NNN) effect in tetranuclear iron(II) complexes of thiacalixarene macrocycles using the isotropic
Heisenberg model has been investigated in order to understand its effects on the observed plateau of magnetization. Although
NNN effect is generally very weak in these kinds of systems, it was calculated that its response is quite significant to the
external perturbations in certain temperature regions. Using the isotropic Heisenberg exchange Hamiltonian, zero-field energy
spectra have been calculated for this particular tetranuclear system. The average magnetic moments with and without next-nearest-neighbour
interactions were also calculated. In order to verify the calculations, the results were compared with experimental data taken
from the literature, whence, it is suggested that observed magnetic behaviour can be improved by taking into account the NNN
effect. 相似文献