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121.
The amino acid analog azaproline (azPro) contains a nitrogen atom in place of the C(alpha) of proline. Peptides containing azPro were shown to stabilize the cis-amide conformer for the acyl-azPro bond and prefer type VI beta-turns both in crystals and in organic solvents by NMR. The increased stability for cis-amide conformers was relatively minor with respect to the trans-conformers. Further, their conformational preferences were depended on solvent. To elucidate the impact of azPro substitution on amide cis-trans isomerism and peptide conformation, this paper reports ab initio studies on azPro derivatives and a comparison with their cognate Pro derivatives: 1-acetyl-2-methyl pyrrolidine (1), 1-acetyl-2-methyl pyrazolidine (2), Ac-Pro-NHMe (3), Ac-azPro-NHMe (4), Ac-azPro-NMe(2) (5), Ac-azAzc-NHMe (6), and Ac-azPip-NHMe (7). Conformational preferences were explored at the MP2/6-31+G** level of theory in vacuo. Solvation effects for 1 and 2 were studied implicitly using the polarizable continuum model and explicitly represented by interactions with a single water molecule. An increase in the conformational preference for the cis-amide conformer of azPro was clearly seen. An intramolecular hydrogen bond occurred solely in the trans-amide conformer that reduced the preference for the cis-conformer by 2.2 kcal/mol. The larger ring homolog aza-pipecolic acid (azPip), in which this internal hydrogen bond was diminished, significantly augmented stabilization of the cis-amide conformer. In aqueous solution, the preference for the cis-amide conformers was greatly reduced, mainly as a result of interaction between water and the lone pair of the alpha-nitrogen in the trans-amide conformer that was 3.8 kcal/mol greater than that in the cis-conformer. In the azPro analog, the energy barrier for cis-trans amide isomerization was 6 kcal/mol less than that in the cognate Pro derivative. Because the azPro derivatives can stabilize the cis-amide bond and mimic a type VI beta-turn without incorporation of additional steric bulk, such a simple chemical modification of the peptide backbone provides a useful conformational constraint when incorporated into the structure of selected bioactive peptides. Such modifications can scan receptors for biological recognition of reverse turns containing cis-amide bonds by the incorporation of type VI beta-turn scaffolds with oriented appended side chains. 相似文献
122.
L.L. Chen H.P. He Z.Z. Ye Y.J. Zeng J.G. Lu B.H. Zhao L.P. Zhu 《Chemical physics letters》2006,420(4-6):358-361
Li-doped ZnO thin films were prepared on glass substrates by DC reactive magnetron sputtering. The influence of post-annealing temperature on the electrical, structural, and optical properties of the films was investigated. A conversion from p-type conduction to n-type in a range of temperature was confirmed by Hall measurement. The optimal p-type conduction is achieved at the annealing temperature of 500 °C with a resistivity of 57 Ω cm, carrier concentration of 1.07 × 1017 cm−3 and Hall mobility of 1.03 cm2 V−1 s−1. From the temperature-dependent PL analysis, the energy level of LiZn acceptor was determined to be 140 meV above the valence band. 相似文献
123.
Stephan?HaiberEmail author Xingtao?Ai Henning?Bubert Moritz?Heintze Volker?Brüser Waltraut?Brandl Gabriela?Marginean 《Analytical and bioanalytical chemistry》2003,375(7):875-883
Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions. 相似文献
124.
A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory. 相似文献
125.
For use in micro-patterned scaffolds in tissue engineering, novel diacrylated triblock macromers (PLA-b-PCL-b-PLA, PGA-b-PCL-b-PGA and PCL-b-PEO-b-PCL) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). All diacrylated polymers were designed as triblock copolymers and involved biodegradable blocks of relatively non-polar epsilon-caprolactone (CL) and polar monomers such as glycolide (GA), lactide (LA) or ethylene oxide (EO). All triblock polymers were prepared in molecular weights of a few kilo daltons via the anionic ring-opening polymerization (ROP) of the corresponding lactide, glycolide or caprolactone using stannous octoate [Sn(Oct)(2)] as catalyst. The polymers had low polydispersity indices, ranging from 1.23 to 1.56. Biodegradable polymeric networks were prepared with conversions of 72-84% via photopolymerization of the triblock diacrylated polymers with 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator. PLA-b-PCL-b-PLA copolymers crumbled easily and were not suitable for micro-patterning. PGA-b-PCL-b-PGA copolymers had higher water contact angles than PCL-b-PEO-b-PCL and were also cytocompatible with Fibroblasts 3T3. 相似文献
126.
A novel mode of affinity chromatography (AC) based on an open tubular capillary column (OTAC) is demonstrated. The OTAC column is prepared by immobilizing Cibacron blue F3GA onto the inner surface of a 50-microm-i.d. capillary column. The AC experiment is performed on a capillary electrophoresis instrument by using its pressure system as the driving force. Bovine serum albumin and lysozyme (Lys) are successfully separated with stepwise gradient elution. The relative standard deviation (RSD) for the elution time of the retained Lys is 0.08%, and good repeatability of its peak area and peak height with an RSD value lower than 2.12% for 10 consecutive runs is observed. The loading capacity and detection limit for the retained Lys are approximately 36 ng and 8.6 ng, respectively. It is also found that the amount of protein adsorbed is unaffected by the flow rate of the loading buffer, and OTAC can be used for the fast determination of biopolymers. Some of the advantages of OTAC over conventional modes of open tubular capillary liquid chromatography are that the detection sensitivity and loading capacity of a sample can be greatly improved, because the relatively large inner diameter of the capillary can be adopted and the whole capillary column can be used to adsorb the solute in OTAC. 相似文献
127.
免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测法测定粮谷中的T-2毒素 总被引:6,自引:0,他引:6
建立了免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测器测定粮谷中T-2毒素含量的方法。样品经甲醇-水(体积比为80∶20)混合溶剂提取,通过免疫亲和柱(IAC)净化,以氰酸蒽(1-AN)为衍生化试剂、4-二甲基氨基吡啶(DMAP)为催化剂进行衍生,以ZORBAX Eclipse XDB-C18 柱为分离柱,乙腈-水(体积比为80∶20)为流动相进行高效液相色谱分离及荧光检测,荧光检测的激发波长为381 nm,发射波长为470 nm。T-2毒素的质量浓度为0.01~1.5 mg/L时与峰高呈良好的线性,相关系数为0.9985。在0.01~1.5 μg/g添加水平下,回收率为79.7%~94.5%,相对标准偏差小于7%;检出限(S/N=3)为0.01 μg/g。该方法净化效果好,灵敏度高,操作简便快速。 相似文献
128.
It is well known that porphyrin derivatives play a key role in the primary process of photo-synthesis[1], in which porphyrins directly absorb the sunlight or indirectly acquire excitation en-ergy from light-harvesting antenna system to reach their excited state, and then donate electrons to quinone acceptors to yield a series of charge-separated species. In general, only first singlet ex-cited state of porphyrins is involved in energy transfer process[2]. However, highly excited state (S2 stat… 相似文献
129.
The direct electron transfer reaction of glucose oxidase (GOx) at a bare silver electrode is verified. The electron transfer number n = 2, electron transfer coefficient α = 0.45 and rate constant of the electrochemical reaction Ks = 0.1 s−1 are obtained. This communication presents a multimolecular adsorption model to explain the properties of the direct electron reaction between GOx and bare silver electrodes. The residual valence force may be an important factor to ensure a direct electron transfer reaction on the bare electrode. On the basis of the experimental fact that only biologically active GOx exhibits electrochemical activity in solution, a facile analytical method for analyzing the active GOx concentration is developed. The results determined correspond very well to that of a spectrometric method. 相似文献
130.
In the analysis of gene expression profiles, the number of tissue samples with genes expression levels available is usually small compared with the number of genes. This can lead either to possible overfitting or even to a complete failure in analysis of microarray data. The selection of genes that are really indicative of the tissue classification concerned is becoming one of the key steps in microarray studies. In the present paper, we have combined the modified discrete particle swarm optimization (PSO) and support vector machines (SVM) for tumor classification. The modified discrete PSO is applied to select genes, while SVM is used as the classifier or the evaluator. The proposed approach is used to the microarray data of 22 normal and 40 colon tumor tissues and showed good prediction performance. It has been demonstrated that the modified PSO is a useful tool for gene selection and mining high dimension data. 相似文献