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1.
2.
Meghan Griffith 《Acta Analytica》2007,22(1):16-28
In this paper, I argue that trying is the locus of freedom and moral responsibility. Thus, any plausible view of free and
responsible action must accommodate and account for free tryings. I then consider a version of agent causation whereby the
agent directly causes her tryings. On this view, the agent is afforded direct control over her efforts and there is no need
to posit—as other agent-causal theorists do—an uncaused event. I discuss the potential advantages of this sort of view, and
its challenges. 相似文献
3.
4.
Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. 相似文献
5.
D. T. Clark J. Peeling J. M. O'Malley 《Journal of polymer science. Part A, Polymer chemistry》1976,14(3):543-551
The surface morphology of a number of films of AB block copolymers of polydimethylsiloxane and polystyrene was examined by ESCA and contact angle measurements. In all cases the immediate surface is shown to consist of an essentially pure polydimethylsiloxane component. By comparing the intensities of elastic peaks corresponding to photoionizations from core levels without energy loss for polydimethylsiloxane and polystyrene with those for the block copolymers and by consideration of shake-up phenomena specific to the polystyrene component, an estimate of the thickness of the polydimethylsiloxane outer layer of the latter may be obtained. This is shown to vary between ~13 and 40 Å, depending on the method of formation of copolymer film. 相似文献
6.
The molecular recognition of peptides and proteins in aqueous solution by designed molecules remains an elusive goal with broad implications for basic biochemical research and for sensors and separations technologies. This paper describes the recognition of N-terminal tryptophan in aqueous solution by the synthetic host cucurbit[8]uril (Q8). Q8 is known to form 1:1:1 heteroternary complexes with methyl viologen (MV) and a second aromatic guest. Here, the complexes of Q8.MV with (i) the four natural aromatic alpha-amino acids, (ii) four singly charged tryptophan derivatives, and (iii) four tryptophan-containing tripeptides were characterized by isothermal titration calorimetry, mass spectrometry, and UV-visible, fluorescence, and (1)H NMR spectroscopy. We find that Q8.MV binds Trp-Gly-Gly with high affinity (K(a) = 1.3 x 10(5) M(-1)), with 6-fold specificity over Gly-Trp-Gly, and with 40-fold specificity over Gly-Gly-Trp. Analysis of the nine indole-containing compounds suggests that peptide recognition is mediated by the electrostatic charge(s) proximal to the indole, and that the mode of binding is consistent for these compounds. Complex formation is accompanied by the growth of a visible charge-transfer band and the quenching of indole fluorescence. These optical properties, combined with the stability and selectivity of this system, are promising for applications in sensing and separating specific peptides. 相似文献
7.
Wagner B. De Almeida Hélio F. Dos Santos Patrick J. O'Malley 《Structural chemistry》1995,6(6):383-389
The potential energy surface (PES) for the herbicide diuron (DCMU), a photosystem II inhibitor, has been extensively investigated using the quantum-mechanical semiempirical molecular orbital methods AM1 and PM3 and molecular mechanics method. A detailed conformational search has been carried out which revealed the occurrence of four genuine minimum energy structures. The relative stability of the conformers and rotational barriers to conformational interconversion were evaluated using distinct theoretical approaches. The results showed that thetrans form of the diuron molecule is more stable than thecis form in all methods, and so it may possibly be the biologically active isomer. 相似文献
8.
We present a novel method for obtaining high resolution NMR spectra in the presence of grossly inhomogeneous magnetic fields, such as those encountered in one-sided access NMR. Our method combines the well-known principle of reference deconvolution with NMR imaging in order to resolve spectral features with frequency resolution orders of magnitude smaller than the prevailing line-broadening due to field inhomogeneity. We demonstrate that, in cases of inhomogeneous field line-broadening more than an order of magnitude larger than the spectral features to be resolved, rather than performing reference deconvolution on the sample as a whole, it is more favourable in terms of SNR to divide the target region of a sample into smaller sub-regions, by means of chemical shift imaging, and then to perform reference deconvolution on the individual sub-region spectra, finally summing the results In this way, significant resolution enhancements can be obtained in the presence of severe magnetic field inhomogeneity without an unacceptable loss in SNR. 相似文献
9.
Sharma PK Reilly MJ Bhatia SK Sakhitab N Archambault JD Bhatia SR 《Colloids and surfaces. B, Biointerfaces》2008,64(2):229-235
Pluronic F127, a triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), has generated considerable interest as a drug delivery vehicle due to its ability to gel at physiological temperatures. This work examines the gelation behavior of Pluronic F127 in the presence of a series of hydrophobic pharmaceuticals, to determine whether there is any correlation between gelation and physicochemical parameters of drug solutes. The study includes the local anesthetics dibucaine, lidocaine, and tetracaine; the pharmaceutical additives methyl paraben, ethyl paraben, and propyl paraben; the anti-cancer agents paclitaxel and baccatin III; and the anti-inflammatory agent sulindac. The results indicate that the presence of local anesthetics and pharmaceutical additives allows F127 solutions to form gels at lower copolymer concentrations; local anesthetics and pharmaceutical additives also shift gelation down to a lower gelation temperature. This behavior is strongly dependent on drug solubility; poorly soluble drugs (paclitaxel, baccatin III, sulindac) do not change the lower gelation temperature or minimum F127 concentration for gelation. An equation relating the decrease in gelation temperature to drug solubility is presented, and the equation fits the data well. The results have significant positive implications on the toxicity and economic issues related to use of Pluronic F127 in drug delivery. 相似文献
10.
Meghan N. Lawson Michael T. Blanda Sara J. Staggs Lauren N. Sederholm David C. Easter 《Journal of Physical Organic Chemistry》2009,22(12):1212-1224
The cone and 1,2,3 alternate isomers of calix[6]arene bis‐crown‐4 were investigated computationally. Structural optimizations, energies, bond distances, and Mulliken charges were calculated by the application of the B3LYP/6‐31g(d) method/basis, followed by NMR calculations via both B3LYP/6‐31g(d) and HF/6‐31g(d). Calculations were completed at three different levels of imposed symmetry, and two calculations investigated the chloroform solvent effects. Better NMR results were obtained from HF/6‐31g(d) calculations that did not impose molecular symmetry constraints. Consideration of solvent effects improved ground state energies, but other improvements were minimal and not significant enough to justify the added computational expense of solvent calculations. Overall results are consistent with known experimental assignments and were valuable for assigning previously unknown NMR peaks. Net charges, electrostatic forces, and local dipoles – but not bond lengths – are strongly correlated to spectroscopic manifestations of steric compression. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献