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991.
992.
Hansen AL Lundström P Velyvis A Kay LE 《Journal of the American Chemical Society》2012,134(6):3178-3189
A Carr-Purcell-Meiboom-Gill relaxation dispersion experiment is presented for quantifying millisecond time-scale chemical exchange at side-chain (1)H positions in proteins. Such experiments are not possible in a fully protonated molecule because of magnetization evolution from homonuclear scalar couplings that interferes with the extraction of accurate transverse relaxation rates. It is shown, however, that by using a labeling strategy whereby proteins are produced using {(13)C,(1)H}-glucose and D(2)O a significant number of 'isolated' side-chain (1)H spins are generated, eliminating such effects. It thus becomes possible to record (1)H dispersion profiles at the β positions of Asx, Cys, Ser, His, Phe, Tyr, and Trp as well as the γ positions of Glx, in addition to the methyl side-chain moieties. This brings the total of amino acid side-chain positions that can be simultaneously probed using a single (1)H dispersion experiment to 16. The utility of the approach is demonstrated with an application to the four-helix bundle colicin E7 immunity protein, Im7, which folds via a partially structured low populated intermediate that interconverts with the folded, ground state on the millisecond time-scale. The extracted (1)H chemical shift differences at side-chain positions provide valuable restraints in structural studies of invisible, excited states, complementing backbone chemical shifts that are available from existing relaxation dispersion experiments. 相似文献
993.
High throughput means to detect and quantify low-frequency mutations (<10(-2) ) in the DNA-coding sequences of human tissues and pathological lesions are required to discover the kinds, numbers, and rates of genetic mutations that (i) confer inherited risk for disease or (ii) arise in somatic tissues as events required for clonal diseases such as cancers and atherosclerotic plaque.While throughput of linear DNA sequencing methods has increased dramatically, such methods are limited by high error rates (>10(-3) ) rendering them unsuitable for the detection of low-frequency risk-conferring mutations among the many neutral mutations carried in the general population or formed in tissue growth and development. In contrast, constant denaturing capillary electrophoresis (CDCE), coupled with high-fidelity PCR, achieved a point mutation detection limit of <10(-5) in exon-sized sequences from human tissue or pooled blood samples. However, increasing CDCE throughput proved difficult due to the need for precise temperature control and the time-consuming optimization steps for each DNA sequence probed. Both of these problems have been solved by the method of cycling temperature capillary electrophoresis (CTCE). The data presented here provide a deeper understanding of the separation principles involved in CTCE and address several elements of a previously presented two-state transport model. 相似文献
994.
Behrens MA Lopez M Kjøniksen AL Zhu K Nyström B Pedersen JS 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1105-1114
A series of thermo-responsive cationic triblock copolymers composed of methoxy-poly(ethylene glycol) (MPEG, hydrophilic), poly(N-isopropylacrylamide) (PNIPAAM, temperature sensitive), and poly((3-acrylamidopropyl) trimethyl ammonium chloride) (PN(+), cationic) has been investigated as a function of temperature and ionic strength. In the MPEG-b-PNIPAAM-b-PN(+) copolymers, the MPEG block length is constant, and the lengths of the PNIPAAM and PN(+) blocks are varied. The solubility of the PNIPAAM block decreases with increasing temperature, and the triblock copolymer thus provides the possibilities of studying micelles with both neutral and charged blocks in the micelle corona as well as the interplay between these two blocks as the electrostatic interactions are varied by addition of salt. Investigation of the systems by densitometry and small-angle X-ray scattering (SAXS) in a temperature range from 20 to 70 °C gave detailed information on the behavior both below and above the critical micelle temperature (CMT). A clear effect of the addition of salt is observed in both the apparent partial specific volume, obtained from the densitometry measurements, and the SAXS data. Below the CMT, the single polymers can be described as Gaussian chains, for which the repulsive interchain interactions, originating from the charged PN(+) block, have to be taken into account in salt-free aqueous solution. Increasing the salt concentration of the solution to 30 mM NaCl leads to an increase in the apparent partial specific volume, and the electrostatic repulsive interchain interactions between the single polymers vanish. Raising the temperature results in micelle formation, except for the copolymer with only 20 NIPAAM units. The SAXS data show that the polymer with the medium PNIPAAM block length forms spherical micelles, whereas the polymer with the longest PNIPAAM block forms cylindrical micelles. Increasing the temperature further above the CMT results in an increase in the micellar aggregation number for both of the polymers forming spherical and cylindrical micelles. The addition of salt to the solution also influences the aggregates formed above the CMT. Overall, the micelles formed in the salt solution have a smaller cross-section radius than those in aqueous solution without added salt. 相似文献
995.
On-line and in situ monitoring of oxygen concentration and gas temperature in a reheating furnace utilizing tunable diode-laser spectroscopy 总被引:1,自引:0,他引:1
Sandström L Malmberg D 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(11):2449-2455
Increased demands on energy savings and quality control in metallurgical processes have created incentives for new methods to monitor and control the process. In this paper we will present a field trial that shows the potential of tunable diode-laser spectroscopy (TDLS) for simultaneous contact free measuring and monitoring of the oxygen concentration as well as the gas temperature in a reheating furnace during production. The field trials were carried out at an oil-fueled reheating furnace during 7 weeks of production. The tunable diode-laser spectrometer was measuring in situ across the preheating zone and the soaking zone in the furnace. During the campaign the oxygen concentration and the gas temperature in the furnace environment were simultaneously monitored and instantaneous variations in these parameters could easily be recorded and subsequently correlated to actual changes in the process. Furthermore, the much shorter response-time of the TDLS technique compared with conventional measurement methods such as thermocouples and extractive gas analyzers was also demonstrated during the trials. The results show the potential for the TDLS technique to be used for energy savings as well as product quality improvements by controlling the burners in the reheating furnace. The results show that it would be possible to control and optimize the oxygen concentration with TDLS in the control loop of the reheating furnace. 相似文献
996.
Abu-Youssef MA Soliman SM Langer V Gohar YM Hasanen AA Makhyoun MA Zaky AH Öhrström LR 《Inorganic chemistry》2010,49(21):9788-9797
[Ag(2-amino-3-methylpyridine)(2)]NO(3) (1) and [Ag(pyridine-2-carboxaldoxime)NO(3)] (2) were prepared from corresponding ligands and AgNO(3) in water/ethanol solutions, and the products were characterized by IR, elemental analysis, NMR, and TGA. The X-ray crystal structures of the two compounds show that the geometry around the silver(I) ion is bent for complex 1 with nitrate as an anion and trigonal planar for complex 2 with nitrate coordinated. ESI-MS results of solutions of 2 indicate the independent existence in solution of the [Ag(pyridine-2-carboxaldoxime)](+) ion. The geometries of the complexes are well described by DFT calculations using the ZORA relativistic approach. The compounds were tested against 14 different clinically isolated and four ATCC standard bacteria and yeasts and also compared with 17 commonly used antibiotics. Both 1 and 2 exhibited considerable activity against S. lutea , M. lutea , and S. aureus and against the yeast Candida albicans , while 2-amino-3-methylpyridine is slightly active and pyridine-2-carboxaldoxime shows no antimicrobial activity. In addition, the interaction of these metal complexes with DNA was investigated. Both 1 and 2 bind to DNA and reduce its electrophoretic mobility with different patterns of migration, while the ligands themselves induce no change. 相似文献
997.
Caraballo R Sakulsombat M Ramström O 《Chemical communications (Cambridge, England)》2010,46(44):8469-8471
Dynamic carbohydrate systems have been efficiently generated through phosphine-mediated disulfide metathesis in aqueous media. The protein compatibility and binding features of the dynamic systems were demonstrated in situ using (1)H STD NMR. 相似文献
998.
国家统计局科研所信息化水平的国际比较研究课题组 《中国信息界》2010,(7):58-66
2001年世界经济论坛推出网络就绪指数(Networked ReadinessIndex,简称NRI),对世界各国(地区)利用信息和通信技术推动经济发展及竞争力的成效进行评估、打分和排名,为分析各国信息化的优劣因素,评价ICT政策和制度环境提供量化的参考依据。 相似文献
999.
Percentages of crude oil, protein, fibre and ash of grape seeds obtained from Turkish cultivars were of the ranges 5.40-10.79, 5.24-7.54, 17.6-27.1, and 1.2-2.6, respectively. The highest crude oil, crude protein and crude fibre were determined in Siyah pekmezlik, Karadimrit and Antep grape seeds. The energy values of seeds were established to be between 102.28 and 148.07?kcal?g(-1). Potassium and calcium contents of seed samples were found to be at high levels compared to sodium. The seeds contained 686-967?ppm of Na, 2468-3618?ppm of K and 2373-4127?ppm of Ca. The refractive index, relative density, acidity, saponification value, unsaponifiable matter and iodine value of seed oils were determined to be in the ranges 1.474-1.477 [Formula: see text], 0.909-0.934 25/25°C, 0.74-1.24%, 181-197, 0.91-1.66%, and 126-135, respectively. The main fatty acids were of the ranges 60.7-68.5% linoleic, 16.1-23.4% oleic and 8.0-10.2% palmitic. The highest percentages of linoleic acid (68.5%) was determined in Siyah pekmezlik seed oil. 相似文献
1000.
Sakulsombat M Zhang Y Ramström O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(20):6129-6132
Dynamic hemithioacetal systems were efficiently generated in organic solvents and subsequently allowed to react with a range of lipases. This resulted in direct, dynamic asymmetric transformation of the systems, leading to optically active 1,3-oxathiolan-5-one products. The tandem process identified lipase-catalyzed lactonization as a useful method for the resolution of optimal constituents with high chemo- and stereoselectivities. 相似文献