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21.
A sensitive 3D NMR pulse scheme, (H)C(CA)NH-COSY, is presented for the assignment of (13)C(delta)(1) Ile chemical shifts in large perdeuterated, methyl-protonated proteins. The nonlinearity of branched amino acids, such as Ile, significantly degrades the quality of TOCSY schemes which transfer magnetization from methyl carbons to the backbone (13)C(alpha) positions, and in applications to high molecular weight proteins (correlation times on the order of 40-50 ns), this compromises the sensitivity of spectra used for methyl assignment. The experiment presented utilizes COSY-based transfer steps and refocuses undesirable (13)C-(13)C scalar couplings that degrade the efficiency of TOCSY transfers. The (H)C(CA)NH-COSY scheme is tested on an (15)N,(13)C,(2)H-[Leu, Val, Ile (delta 1 only)]-methyl-protonated maltose binding protein (MBP)/beta-cyclodextrin complex at 5 degrees C (molecular tumbling time 46 +/- 2 ns), facilitating the assignment of (13)C(delta 1) chemical shifts for 18 of the 19 Ile residues for which backbone assignments were previously obtained. Both sensitivity and resolution of the resulting spectra are shown to be significantly better than those for a similar TOCSY-based approach. 相似文献
22.
Miles S. CongreveCorinne Kay Jan J. ScicinskiSteven V. Ley Geoffrey WilliamsPeter J. Murray Stephen C. McKeownStephen P. Watson 《Tetrahedron letters》2003,44(21):4153-4156
The development of a versatile amine releasing linker based on the modified o-nitrobenzene sulfonamide protective group is described. This new N-Boc-o-nitrobenzenesulfonamide (Boc-ONBS) linker enables the elaboration on resin of primary and secondary amines by sequential substitution of the sulfonamide moiety using the Mitsunobu reaction. A 16-member array of secondary and Boc protected primary amines was then prepared using this linker. 相似文献
23.
Bernard S. Kay 《Communications in Mathematical Physics》1978,62(1):55-70
We give mathematically rigorous results on the quantization of the covariant Klein Gordon field with an external stationary scalar interaction in a stationary curved space-time. We show how, following Segal, Weinless etc., the problem reduces to finding a “one particle structure” for the corresponding classical system. Our main result is an existence theorem for such a one-particle structure for a precisely specified class of stationary space-times. Byproducts of our approach are:
- A discussion of when a given “equal-time” surface in a given stationary space-time is Cauchy.
- A modification and extension of the methods of Chernoff [3] for proving the essential self-adjointness of certain partial differential operators.
24.
An (15)N NMR R(1rho) relaxation experiment is presented for the measurement of millisecond time scale exchange processes in proteins. On- and off-resonance R(1rho) relaxation profiles are recorded one residue at a time using a series of one-dimensional experiments in concert with selective Hartmann-Hahn polarization transfers. The experiment can be performed using low spin-lock field strengths (values as low as 25 Hz have been tested), with excellent alignment of magnetization along the effective field achieved. Additionally, suppression of the effects of cross-correlated relaxation between dipolar and chemical shift anisotropy interactions and (1)H-(15)N scalar coupled evolution is straightforward to implement, independent of the strength of the (15)N spin-locking field. The methodology is applied to study the folding of a G48M mutant of the Fyn SH3 domain that has been characterized previously by CPMG dispersion experiments. It is demonstrated through experiment that off-resonance R(1rho) data measured at a single magnetic field and one or more spin-lock field strengths, with amplitudes on the order of the rate of exchange, allow a complete characterization of a two-site exchange process. This is possible even in the case of slow exchange on the NMR time scale, where complementary approaches involving CPMG-based experiments fail. Advantages of this methodology in relation to other approaches are described. 相似文献
25.
Tatsuhiko Nakano A.C. Spinelli A. Martín A. Usubillaga Andrew T. McPhail Kay D. Onan 《Tetrahedron letters》1982,23(35):3627-3630
cleavage of the epoxide () of methyl (-)-kaur-9(11)-en-19-oate () with boron trifluoride-ether in benzene and in acetic anhydride yielded () and (), respectively. On epoxidation with -chloroperbenzoic acid in the presence of -nitrosomethyl urea, () suffered a backbone rearrangement to form (). 相似文献
26.
Daschbach JL Dohnalek Z Liu SR Smith RS Kay BD 《The journal of physical chemistry. B》2005,109(20):10362-10370
The adsorption of water on FeO(111) is investigated using temperature programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRAS). Well-ordered 2 ML thick FeO(111) films are grown epitaxially on a Pt(111) substrate. Water adsorbs molecularly on FeO(111) and desorbs with a well resolved monolayer peak. IRAS measurements as a function of coverage are performed for water deposited at 30 and 135 K. For all coverages (0.2 ML and greater), the adsorbed water exhibits significant hydrogen bonding. Differences in IRAS spectra for water adsorbed at 30 and 135 K are subtle but suggest that water adsorbed at 135 K is well ordered. Monolayer nitrogen TPD spectra from water covered FeO(111) surfaces are used to investigate the clustering of the water as a function of deposition or annealing temperature. Temperature dependent water overlayer structures result from differences in water diffusion rates on bare FeO(111) and on water adsorbed on FeO(111). Features in the nitrogen TPD spectra allow the monolayer wetting and 2-dimensional (2D) ordering of water on FeO(111) to be followed. Voids in a partially disordered first water layer exist for water deposited below 120 K and ordered 2D islands are found when depositing water above 120 K. 相似文献
27.
Han Z Karatan E Scholle MD McCafferty J Kay BK 《Combinatorial chemistry & high throughput screening》2004,7(1):55-62
When using multiple targets and libraries, selection of affinity reagents from phage-displayed libraries is a relatively time-consuming process. Herein, we describe an automation-amenable approach to accelerate the process by using alkaline phosphatase (AP) fusion proteins in place of the phage ELISA screening and subsequent confirmation steps with purified protein. After two or three rounds of affinity selection, the open reading frames that encode the affinity selected molecules (i.e., antibody fragments, engineered scaffold proteins, combinatorial peptides) are amplified from the phage or phagemid DNA molecules by PCR and cloned en masse by a Ligation Independent Cloning (LIC) method into a plasmid encoding a highly active variant of E. coli AP. This time-saving process identifies affinity reagents that work out of context of the phage and that can be used in various downstream enzyme linked binding assays. The utility of this approach was demonstrated by analyzing single-chain antibodies (scFvs), engineered fibronectin type III domains (FN3), and combinatorial peptides that were selected for binding to the Epsin N-terminal Homology (ENTH) domain of epsin 1, the c-Src SH3 domain, and the appendage domain of the gamma subunit of the clathrin adaptor complex, AP-1, respectively. 相似文献
28.
Microwave irradiation of alkynyl allenes affords an intramolecular [2 + 2] cycloaddition reaction. This cycloaddition provides an efficient route to bicyclomethylenecyclobutenes. The reaction occurs with complete regioselectivity for the distal double bond of the allene for the selective formation of a variety of hetero- and carbocyclic substrates. Bicyclo[4.2.0]octadienes and bicyclo[5.2.0]nonadienes have been prepared in high yield. [reaction: see text] 相似文献
29.
Altieri A Gatti FG Kay ER Leigh DA Martel D Paolucci F Slawin AM Wong JK 《Journal of the American Chemical Society》2003,125(28):8644-8654
A series of [2]rotaxanes containing succinamide and naphthalimide hydrogen-bonding stations for a benzylic amide macrocycle is described. Electrochemical reduction and oxidation of the naphthalimide group alters its ability to form hydrogen bonds to the macrocycle to such a degree that redox processes can be used to switch the relative macrocycle-binding affinities of the two stations in a rotaxane by over 8 orders of magnitude. The structure of the neutral [2]rotaxane in solution is established by (1)H NMR spectroscopy and shows that the macrocycle exhibits remarkable positional integrity for the succinamide station in a variety of solvents. Cyclic voltammetry experiments allow the simultaneous stimulation and observation of a redox-induced dynamic process in the rotaxane which is both reversible and cyclable. Model compounds in which various conformational and co-conformational changes are prohibited demonstrate unequivocally that the redox response is the result of shuttling of the macrocycle between the two stations. At room temperature in tetrahydrofuran the electrochemically induced movement of the macrocycle between the two stations takes approximately 50 micros. 相似文献
30.
Tugarinov V Hwang PM Ollerenshaw JE Kay LE 《Journal of the American Chemical Society》2003,125(34):10420-10428
A comparison of HSQC and HMQC pulse schemes for recording (1)H[bond](13)C correlation maps of protonated methyl groups in highly deuterated proteins is presented. It is shown that HMQC correlation maps can be as much as a factor of 3 more sensitive than their HSQC counterparts and that the sensitivity gains result from a TROSY effect that involves cancellation of intra-methyl dipolar relaxation interactions. (1)H[bond](13)C correlation spectra are recorded on U-[(15)N,(2)H], Ile delta 1-[(13)C,(1)H] samples of (i) malate synthase G, a 723 residue protein, at 37 and 5 degrees C, and of (ii) the protease ClpP, comprising 14 identical subunits, each with 193 residues (305 kDa), at 5 degrees C. The high quality of HMQC spectra obtained in short measuring times strongly suggests that methyl groups will be useful probes of structure and dynamics in supramolecular complexes. 相似文献