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31.
Frederick MO Mulder JA Tracey MR Hsung RP Huang J Kurtz KC Shen L Douglas CJ 《Journal of the American Chemical Society》2003,125(9):2368-2369
A copper-catalyzed new C-N bond formation involving a sp-hybridized carbon is described here leading to a facile entry for syntheses of chiral ynamides. This direct N-alkynylation of amides should have a significant impact on the future development of synthetic methodologies employing ynamides. 相似文献
32.
Wong JW Maleknia SD Downard KM 《Journal of the American Society for Mass Spectrometry》2005,16(2):225-233
The calcium-dependent interaction of calmodulin and melittin is studied through the application of a radical probe approach in which solutions of the protein and peptide and protein alone are subjected to high fluxes of hydroxyl and other oxygen radicals on millisecond timescales. These radicals are generated by an electrical discharge within an electrospray ion source of a mass spectrometer. Condensation of the electrosprayed droplets followed by proteolytic digestion of both calmodulin and melittin has identified residues in both which participate in the interaction and/or are shielded from solvent within the protein complex. Consistent with other theoretical models and available experimental data, the tryptophan residue of melittin at position 19 is shown to be critical to the formation of the complex with the C-terminal domain of peptide enveloped by and protected from oxidation upon binding to the protein. Furthermore, the N-terminal domain (to residue 36) and tyrosine at position 99 in calmodulin are significantly protected from limited oxidation upon the binding of melittin while exposing the phenylalanine residue at position 92 of the flexible loop domain. The N-terminus (through residue 36) of calmodulin is shown to lie in closer proximity to the melittin helix than its C-terminal counterpart (residues 127-148) based upon the protection levels measured at reactive residues within these segments of the protein. 相似文献
33.
Sameer Chavda Elliot Coulbeck Gregory S. Coumbarides Marco Dingjan Jason Eames Stephanos Ghilagaber Yonas Yohannes 《Tetrahedron: Asymmetry》2006,17(24):3386-3399
The resolution of 2-phenylpropanoyl chloride using an equimolar combination of quasi-enantiomeric oxazolidinones is discussed. The levels of diastereoselectivity were found to be dependent upon the structural nature of the metallated oxazolidinone, temperature and metal counter-ion. 相似文献
34.
Gonzales JM Barden CJ Brown ST Schleyer Pv Schaefer HF Li QS 《Journal of the American Chemical Society》2003,125(4):1064-1071
The adiabatic electron affinities of cyclopentadiene and 10 associated benzannelated derivatives have been predicted with both density functional and Hartree-Fock theory. These systems can also be regarded as benzenoid polycyclic aromatic hydrocarbons (PAHs) augmented with five-membered rings. Like the PAHs, the electron affinities of the present systems generally increase with the number of rings. To unequivocally bind an electron, cyclopentadiene must have at least two conventionally fused benzene rings. 1H-Benz[f]indene, a naphthalene-annulated cyclopentadiene, is predicted to have a zero-point energy corrected adiabatic electron affinity of 0.13 eV. Since the experimental E(A) of naphthalene is negative (-0.19 eV), the five-membered ring appendage contributes to the stability of the naphthalene-derived 1H-benz[f]indene radical anion significantly. The key to binding the electron is a contiguous sequence of fused benzenes, since fluorene, the isomer of 1H-benz[f]indene, with separated six-membered rings, has an electron affinity of -0.07 eV. Each additional benzene ring in the sequence fused to cyclopentadiene increases the electron affinity by 0.15-0.65 eV: the most reliable predictions are cyclopentadiene (-0.63 eV), indene (-0.49 eV), fluorene (-0.07 eV), 1H-benz[f]indene (0.13 eV), 1,2-benzofluorene (0.25 eV), 2,3-benzofluorene (0.26 eV), 12H-dibenzo[b,h]fluorene (0.65 eV), 13H-indeno[1,2-b]anthracene (0.82 eV), and 1H-cyclopenta[b]naphthacene (1.10 eV). In contrast, if the six-membered ring-fusion is across the C(2)-C(3) cyclopentadiene single bond, only a single benzene is needed to bind an electron. The theoretical electron affinity of the resulting molecule, isoindene, is 0.49 eV, and this increases to 1.22 eV for 2H-benz[f]indene. The degree of aromaticity is responsible for this behavior. While the radical anions are stabilized by conjugation, which increases with the size of the system, the regular indenes, like PAHs in general, suffer from the loss of aromatic stabilization in forming their radical anions. While indene is 21 kcal mol(-1) more stable than isoindene, the corresponding radical anion isomers have almost the same energy. Nucleus-independent chemical shift calculations show that the highly aromatic molecules lose almost all aromaticity when an extra electron is present. The radical anions of cyclopentadiene and all of its annulated derivatives have remarkably low C-H bond dissociation energies (only 18-34 kcal mol(-1) for the mono-, bi-, and tricyclics considered). Hydrogen atom loss leads to the restoration of aromaticity in the highly stabilized cyclopentadienyl anion congeners. 相似文献
35.
Despite the popularity of boron and silicon allylation reagents in stereocontrolled synthesis, they suffer from a number of inherent limitations that have slowed down their development as synthetic tools for nucleophilic additions to carbonyl compounds and imine derivatives. These limitations are the low reactivity and diastereoselectivity of allyl trialkylsilane reagents, and the lack of catalytic systems for the activation and substoichiometric control of enantioselectivity in the additions of allyl boron reagents. To develop more efficient and general methods for the control of absolute stereochemistry in the resulting homoallylic alcohols, new approaches aimed at solving the problem of activation of allylic boron and silicon reagents are needed. This Minireview describes a number of recent approaches that have been devised to address this problem. 相似文献
36.
Seasonal fluctuation of DNA photodamage in marine plankton assemblages at Palmer Station, Antarctica
Meador J Jeffrey WH Kase JP Pakulski JD Chiarello S Mitchell DL 《Photochemistry and photobiology》2002,75(3):266-271
Ultraviolet radiation-induced DNA damage frequencies were measured in DNA dosimeters and natural plankton communities during the austral spring at Palmer Station, Antarctica, during the 1999-2000 field season. We found that the fluence of solar ultraviolet-B radiation (UV-B) at the earth's surface correlated with stratospheric ozone concentrations, with significant ozone depletion observed because of "ozone hole" conditions. To verify the interdependence of ozone depletion and DNA damage in natural microbial communities, seawater was collected daily or weekly from Arthur Harbor at Palmer Station, Antarctica, throughout "ozone season," exposed to ambient sunlight between 0600 and 1800 h and fractionated using membrane filtration to separate phytoplankton and bacterioplankton populations. DNA from these fractions was isolated and DNA damage measured using radioimmunoassay. Under low-ozone conditions cyclobutane dimer concentrations in bacterioplankton and phytoplankton communities were maximal. DNA damage measured in dosimeters correlated closely with ozone concentrations and UV-B fluence. Our studies offer further support to the theory that stratospheric deozonation is detrimental to marine planktonic organisms in the Southern Ocean. 相似文献
37.
Chemosensors for the marine toxin saxitoxin 总被引:1,自引:0,他引:1
Gawley RE Pinet S Cardona CM Datta PK Ren T Guida WC Nydick J Leblanc RM 《Journal of the American Chemical Society》2002,124(45):13448-13453
Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed. 相似文献
38.
Hill RT Lyon JL Allen R Stevenson KJ Shear JB 《Journal of the American Chemical Society》2005,127(30):10707-10711
The functionality and structural diversity of biological macromolecules has motivated efforts to exploit proteins and DNA as templates for synthesis of electronic architectures. Although such materials offer promise for numerous applications in the fabrication of cellular interfaces, biosensors, and nanoelectronics, identification of techniques for positioning and ordering bioelectronic components into useful patterns capable of sophisticated function has presented a major challenge. Here, we describe the fabrication of electronic materials using biomolecular scaffolds that can be constructed with precisely defined topographies. In this approach, a tightly focused pulsed laser beam capable of promoting protein photo-cross-linking in specified femtoliter volume elements is scanned within a protein solution, creating biomolecular matrices that either remain in integral contact with a support surface or extend as free-standing structures through solution, tethered at their ends. Once fabricated, specific protein scaffolds can be selectively metallized via targeted deposition and growth of metal nanoparticles, yielding high-conductivity bioelectronic materials. This aqueous fabrication strategy opens new opportunities for creating electronic materials in chemically sensitive environments and may offer a general approach for creating microscopically defined inorganic landscapes. 相似文献
39.
The creation and use of unnatural molecules to control cellular function is a long standing goal of the chemical community, but in general, these efforts have been directed at finding molecules to inhibit or activate a particular molecular target or function, or to elicit a particular phenotype. Here we show that multiple unnatural molecules (orthogonal ribosomes) can be used combinatorially, in a single cell, to program Boolean logic functions. These experiments show how attention to the molecular specificity of noncovalent interactions between unnatural macromolecules allows the synthesis of complex function from the "bottom-up" in living matter. 相似文献
40.
[structure: see text] Thiophene dendrons and dendrimers were designed and synthesized using a convergent approach. Metal-mediated coupling reactions were used in the synthesis. A rational approach allowed the formation of alphaalpha, betabeta, and alphabeta linkages between the dendrons and thiophene units. 相似文献