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991.
A novel kinetic process was investigated for functionalizing "on-demand" local regions of well-defined linear polystyrene chains. This concept relies on the atom transfer radical copolymerization (ATRP) of functional N-substituted maleimides with styrene. This copolymerization is a controlled radical process, which combines two unique kinetic features: i) all the polymers chains are growing simultaneously and ii) the cross-propagation of the comonomers is highly-favored as compared to homopolymerization. Thus, discrete amounts of N-substituted maleimides (e.g., 1 equiv as compared to initiator) are consumed extremely fast in the copolymerization process and are therefore locally incorporated in narrow regions of the growing polystyrene chains. MALDI-TOF analysis of model copolymers indicated that this kinetic concept is efficient. Although a sequence distribution is observed, well-defined polymer chains having only one or two functional maleimide units per chain were found to be the most abundant species. Furthermore, the position of the functional groups in the polystyrene chains can be kinetically-controlled by adding the N-substituted maleimides at desired times during the course of the polymerization. This method is very versatile and can be applied to a wide variety of N-substituted maleimides. Herein, a library of 20 different maleimides bearing various functional groups (e.g., aromatic moieties, fluorinated groups, hydroxy functions, protected esters, protected amines, light-responsive moieties, fluorophores and biorelevant functions such as short poly(ethylene glycol) segments or biotin moieties) was investigated. In most cases, the functional N-substituted maleimides could be efficiently incorporated in the polystyrene chains. 相似文献
992.
Kalkhof S Haehn S Ihling C Paulsson M Smyth N Sinz A 《Rapid communications in mass spectrometry : RCM》2008,22(12):1933-1940
The disulfide bonding patterns in the N-terminal (LN) domains of the basement membrane protein laminin beta1 have not been investigated so far. We report an in-depth mass spectrometric analysis using offline nano-high-performance liquid chromatography/matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry (nano-HPLC/MALDI-TOF/TOF-MS) for determining the disulfide bond patterns in the LN-domain of recombinant mouse laminin beta1 chain for the first time. Mass spectra were recorded and the putatively disulfide-linked peptides were subjected to LIFT-TOF/TOF-MS to confirm the disulfide bond. Screening the fragment ion mass spectra of disulfide-linked peptides for characteristic 66-amu patterns (34 u +32 u), arising from symmetric and asymmetric cleavage of disulfide bonds, facilitated their identification. Using various enzymes for proteolytic digestion of a recombinant laminin beta1 chain N-terminal protein fragment, a linear bonding pattern of the eight cysteine residues in the LN-domain of the laminin beta1 chain was observed with a (1-2, 3-4, 5-6, 7-8) connectivity of cysteines. The identical disulfide-bonding pattern was found in E4, the N-terminal laminin beta1 chain fragment derived by elastase digestion of mouse tumor laminin-111, confirming that this pattern also occurs in native laminin. 相似文献
993.
Prokofieva A Prikhod'ko AI Dechert S Meyer F 《Chemical communications (Cambridge, England)》2008,(8):1005-1007
A highly preorganized bioinspired dicopper complex with imidazole ligation catalyzes the selective benzylic para-C-H activation of 2,4,6-trimethylphenol under aerobic conditions, yielding either the stilbenequinone or 4-methoxymethyl-2,6-dimethylphenol depending on the solvent used. 相似文献
994.
Sinnwell S Inglis AJ Davis TP Stenzel MH Barner-Kowollik C 《Chemical communications (Cambridge, England)》2008,(17):2052-2054
The tendency of electron-deficient dithioesters to undergo hetero Diels-Alder cycloadditions is successfully used to generate polymer conjugates between a RAFT-polymerized poly(styrene) and a diene-terminated poly(epsilon-caprolactone). 相似文献
995.
Michael Dom Jiong Guo Rolf Niedermeier Sebastian Wernicke 《Journal of Discrete Algorithms》2008,6(3):393-407
Set Cover problems are of core importance in many applications. In recent research, the “red-blue variants” where blue elements all need to be covered whereas red elements add further constraints on the optimality of a covering have received considerable interest. Application scenarios range from data mining to interference reduction in cellular networks. As a rule, these problem variants are computationally at least as hard as the original set cover problem. In this work we investigate whether and how the well-known consecutive ones property, restricting the structure of the input sets, makes the red-blue covering problems feasible. We explore a sharp border between polynomial-time solvability and NP-hardness for these problems. 相似文献
996.
997.
Five recently synthesized pyridinium ionic liquids [(1-butyl-4-methylpyridinium, 1-octylpyridinium, 1-octyl-2-methylpyridinium, 1-octyl-3-methylpyridinium, and 1-octyl-4-methylpyridinium, all with anion bis(trifluoromethylsulfonyl)imide], were investigated to establish the influence of substituting a methyl group and the influence of alkyl chain length on the cation on polarity ET(N) and on three Kamlet-Taft parameters: dipolarity/polarizabilty (pi*), hydrogen-bond acidity (alpha), and hydrogen-bond basicity (beta). Experimental measurements cover the range 25 to 65 degrees C. 相似文献
998.
A practical method for the synthesis of gem-2,2-disubstituted tertiary amines from the corresponding lactams (or amides) is reported. It is based on the reaction of thioiminium ions, easily prepared from lactams and amides with organometallic reagents such allylmagnesium, benzylmagnesium, and primary alkylcerium reagents. 相似文献
999.
Asymmetric 1,4-addition of arylboronic acids to (E)-methyl 2-cyano-3-arylpropenoates proceeded in the presence of a rhodium catalyst (3 mol %) coordinated with a chiral diene ligand, (R,R)-Ph-bod*, to give high yields of the corresponding methyl 3,3-diaryl-2-cyanopropanoates with high enantioselectivity (up to 99% ee). This catalytic asymmetric transformation was applied to the asymmetric synthesis of (R)-tolterodine. 相似文献
1000.
The 1,3-alternate 25,27-bis-[p-chlorobenzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene-bonded silica gel stationary phase was synthesized, structurally characterized, and used as a selector in high performance liquid chromatography. Selectivity studies on that phase used aromatic positional isomers, alkylbenzenes, polynuclear aromatic hydrocarbons, sulfonamides, and non-steroidal anti-inflammatory drugs as analytes. The effects of organic modifier content and pH of the mobile phase on retention and selectivity of selected aromatic positional isomers were studied. Selectivity comparisons of the novel phase vs. 1,3-alternate 25,27-di-[benzyloxy]-26,28-bis-[3-propyloxy]-calix[4]arene phase and commercially available RP-Phenyl phases were performed. The retention mechanism was also discussed. The results indicated that the calixarene stationary phase behaves like a reversed-phase packing; however, other retention mechanisms seem to be involved in the separation process. 相似文献