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排序方式: 共有321条查询结果,搜索用时 140 毫秒
131.
Andrew C. Benniston Anthony HarrimanSongjie Yang Ross W. Harrington 《Tetrahedron letters》2011,52(41):5315-5318
The synthesis of a highly-strained cyclophane comprising azobenzene and methyl viologen units was achieved by coupling 3,3′-dihydroxy-4,4′-bipyridine with azobenzoic acid in CH2Cl2. The molecular structure, determined by single-crystal X-ray crystallography, shows that the azobenzene NN unit adopts the trans conformation and that the bipyridinium unit is twisted. The cyclic voltammogram recorded for the target compound displays an irreversible wave at −0.37 V vs Ag/AgCl, associated with the one-electron reduction of the bipyridinium subunit. A further wave is seen at E1/2 = −1.52 V versus Ag/AgCl and is assigned to one-electron reduction of the azobenzene group. Visible light illumination of the azobenzene chromophore in CH3CN triggers trans to cis isomerization but the process is irreversible. 相似文献
132.
Wang Z Zhang Y Zhang H Harrington PB Chen H 《Journal of the American Society for Mass Spectrometry》2012,23(3):520-529
We previously reported that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used to selectively derivatize thiols for mass spectrometric analysis, and the introduced
selenium tags are useful as they could survive or removed with collision-induced dissociation (CID). Described herein is the
further study of the reactivity of various protein/peptide thiols toward NPSP and its application to derivatize thiol peptides
in protein digests. With a modified protocol (i.e., dissolving NPSP in acetonitrile instead of aqueous solvent), we found
that quantitative conversion of thiols can be obtained in seconds, using NPSP in a slight excess amount (NPSP:thiol of 1.1–2:1).
Further investigation shows that the thiol reactivity toward NPSP reflects its chemical environment and accessibility in proteins/peptides.
For instance, adjacent basic amino acid residues increase the thiol reactivity, probably because they could stabilize the
thiolate form to facilitate the nucleophilic attack of thiol on NPSP. In the case of creatine phosphokinase, the native protein
predominately has one thiol reacted with NPSP while all of four thiol groups of the denatured protein can be derivatized,
in accordance with the corresponding protein conformation. In addition, thiol peptides in protein/peptide enzymatic digests
can be quickly and effectively tagged by NPSP following tri-n-butylphosphine (TBP) reduction. Notably, all three thiols of the peptide QCCASVCSL in the insulin peptic digest can be modified
simultaneously by NPSP. These results suggest a novel and selective method for protecting thiols in the bottom-up approach
for protein structure analysis. 相似文献
133.
Giri N Clegg W Harrington RW Horton PN Hursthouse MB James SL 《Chemical communications (Cambridge, England)》2012,48(34):4061-4063
Instead of highly symmetrical T-symmetry cages common in self-assembly, the p-NMe(2)-substituted triphosphine CH(3)C{CH(2)P(4-C(6)H(4)NMe(2))(3) gives open, polar C(3) symmetry cages [Ag(6)(triphos)(4)X(3)](3+) which lack one of the expected face-capping anions; despite its subtlety this difference occurs selectively in solution and two examples have been crystallographically characterised. 相似文献
134.
Coyle L Middleton PS Murphy CJ Clegg W Harrington RW Errington RJ 《Dalton transactions (Cambridge, England : 2003)》2012,41(3):971-981
The tetra-n-butylammonium (TBA) salts of [((i)PrO)TiMo(5)O(18)](3-) 1 and [((i)BuO)TiMo(5)O(18)](3-) 2 were prepared by hydrolysis of mixtures of (TBA)(2)[Mo(2)O(7)], (TBA)(4)α-[Mo(8)O(26)] and Ti(OR)(4) (R = (i)Pr or (i)Bu) in acetonitrile. Treatment of (TBA)(3)1 with alcohols ROH afforded primary and tertiary alkoxide derivatives [(RO)TiMo(5)O(18)](3-) (R = Me 3, (t)Bu 4), whilst aryloxides [(ArO)TiMo(5)O(18)](3-) were prepared by reacting 1 with phenols ArOH (Ar = C(6)H(4)Me-4 5, and C(6)H(4)CHO-2 6). Oxo-bridged [(μ-O)(TiMo(5)O(18))(2)](6-)7 rather than the hydroxo derivative [(HO)TiMo(5)O(18)](3-) was obtained upon hydrolysis of 1. X-Ray crystal structures of TBA salts of anions 3-7 show that titanium is six-coordinate in all cases, although titanium sites are disordered over two trans positions in 3. Mo-O bond length alternation is observed in the Mo(4)O(4) planes of 4 and 7 and in one of the two independent anions in the structure of 3. In solution, (17)O NMR spectra are consistent with the higher anionic charge compared to [Mo(6)O(19)](2-) and reveal an order of basicity for the anions [LM'Mo(5)O(18)](3-) associated with the ability of {LM'}(3+) to donate/withdraw electron density from {Mo(5)O(18)}(6-). Protonolysis reactions of 1 and 3 were slower than for tungstate analogues and the possibility of initial protonation at TiOM (M = Mo) rather than TiOR (M = W) in a proton-assisted S(N)1 mechanism for ligand exchange in [(RO)TiM(5)O(18)](3-) is discussed. 相似文献
135.
Peter de B. Harrington Kent J. Voorhees Franco Basile Alan D. Hendricker 《Journal of the American Society for Mass Spectrometry》2002,13(1):10-21
Temperature constrained cascade correlation networks (TCCCNs) are computational neural networks that configure their own architecture, train rapidly, and give reproducible prediction results. TCCCN classification models were built using the Latin-partition method for five classes of pathogenic bacteria. Neural networks are problematic in that the relationships among the inputs (i.e., mass spectra) and the outputs (i.e., the bacterial identities) are not apparent. In this study, neural network models were constructed that successfully classified the targeted bacteria and the classification model was validated using sensitivity and target transformation factor analysis (TTFA). Without validation of the classification model, it is impossible to ascertain whether the bacteria are classified by peaks in the mass spectrum that have no causal relationships with the bacteria, but instead randomly correlate with the bacterial classes. Multiple single output network models did not offer any benefits when compared to single network models that had multiple outputs. A multiple output TCCCN model achieved classification accuracies of 96 +/- 2% and exhibited improved performance over multiple single output TCCCN models. Chemical ionization mass spectra were obtained from in situ thermal hydrolysis methylation of freeze-dried bacteria. Mass spectral peaks that pertain to the neural network classification model of the pathogenic bacterial classes were obtained by sensitivity analysis. A significant number of mass spectral peaks that had high sensitivity corresponded to known biomarkers, which is the first time that the significant peaks used by a neural network model to classify mass spectra have been divulged. Furthermore, TTFA furnishes a useful visual target as to which peaks in the mass spectrum correlate with the bacterial identities. 相似文献
136.
Benniston AC Winstanley TP Lemmetyinen H Tkachenko NV Harrington RW Wills C 《Organic letters》2012,14(6):1374-1377
The synthesis of dyes based on a highly substituted terephthalic acid core is described, starting from readily available 2,5-dihydroxy-terephthalic acid diethyl ester. The dyes are highly colored, soluble in organic solvents and reasonably fluorescent in solution and in the solid state. The maxima for absorption and emission are around 402 and 502 nm, respectively. The fluorophores are readily cyclized to generate compounds which comprise the basic 6,13-dihydroxy-chromeno[2,3-b]xanthene-7,14-dione unit. These new derivatives are nonfluorescent. 相似文献
137.
离子淌度谱(IMS)是检测痕量挥发性有机化合物的灵敏方法。SIMPLISMA(simpletouseinteractiveselfmodelingmixtureanalysis)是一种自模型曲线分辨方法。文章将SIMPLISMA用于DMMP,DIMP和DEMP的IMS检测和数据的处理。这些化合物的IMS谱数据经SIMPLISMA处理后,可以提取出IMS的谱特征,并去除大部分噪声的影响。经SIMPLISMA提取的IMS谱可被用于其他计算,如曲线分辨和模式识别等。 相似文献
138.
Evaluation of stresses in structures such as bridges, buildings, pipelines and railways is challenging because the loads cannot easily be manipulated to allow direct measurements. This paper focuses on the development of a method that combines the hole-drilling technique with Digital Image Correlation (DIC) to evaluate these difficult-to-measure structural stresses. The hole-drilling technique works by relating local displacements caused by the removal of a small amount of stressed material to the original stresses within the drilled hole. Adaptation of this method to measure structural stresses requires scaling up the hole size and modifying the calculation approach to measure deeper into a material. DIC provides a robust means to measure full-field displacements that can easily be scaled to different hole sizes and corrected for typical artifacts that occur in practical on-site measurements. There are two primary areas of investigation: the adaptation of the DIC/hole-drilling method to measure structural stresses and the development of a correction method to remove coexisting stresses such as residual and machining stresses from the measurement. Experimental measurements are made to demonstrate the measurement method on different structure types including the example practical problem of measuring thermally induced stresses in railroad tracks. 相似文献
139.
Harrington J Kleber F Reubold U 《The Journal of the Acoustical Society of America》2008,123(5):2825-2835
The aim of the study was to establish whether /u/-fronting, a sound change in progress in standard southern British, could be linked synchronically to the fronting effects of a preceding anterior consonant both in speech production and speech perception. For the production study, which consisted of acoustic analyses of isolated monosyllables produced by two different age groups, it was shown for younger speakers that /u/ was phonetically fronted and that the coarticulatory influence of consonants on /u/ was less than in older speakers. For the perception study, responses were elicited from the same subjects to two minimal word-pair continua that differed in the direction of the consonants' coarticulatory fronting effects on /u/. Consistent with their speech production, young listeners' /u/ category boundary was shifted toward /i/ and they compensated perceptually less for the fronting effects of the consonants on /u/ than older listeners. The findings support Ohala's model in which certain sound changes can be linked to the listener's failure to compensate for coarticulation. The results are also shown to be consistent with episodic models of speech perception in which phonological frequency effects bring about a realignment of the variants of a phonological category in speech production and perception. 相似文献
140.