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991.
Miranda LP Lubell WD Halkes KM Groth T Grøtli M Rademann J Gotfredsen CH Meldal M 《Journal of combinatorial chemistry》2002,4(5):523-529
A novel polymer matrix for solid-phase synthesis, SPOCC(194) resin (1), was designed featuring a backbone of homogeneous tetraethylene glycol (TEG(194)) macromonomer linked by quaternary carbon junctions and terminating in primary alcohol functionality. Beaded SPOCC(194) resin was effectively prepared by suspension polymerization of oxetanylated TEG macromonomer 5 in stirred silicon oil. Mechanically stable and inert to a diverse range of reaction conditions, SPOCC(194) possessed a high hydroxyl group loading (0.9-1.2 mmol/g) for substrate attachment and swelled effectively ( approximately 2-4 mL/g) in a variety of organic and aqueous solvents. Developed for solid-phase synthesis at high reactant concentrations for driving organic and aqueous reactions to completion, SPOCC(194) exhibited high functional group density (mmol/mL) similar to that of low-loaded aminomethylated polystyrene-divinylbenzene copolymer (PS-1%DVB) yet significantly higher than that of PEGA(1900), SPOCC(1500), and TentaGel S. High-resolution MAS NMR spectra of Fmoc-derivatized SPOCC(194) indicate that monitoring of functional group transformation is possible. Moreover, by employment of a nonaromatic resin-linker combination, electrophilic chemistry, such as Lewis acid catalyzed glycosylation and Friedel-Crafts acylation, was selectively performed on substrate bound to SPOCC(194) resin. Such properties make SPOCC(194) resin a promising new polymer matrix for the support-bound construction of small organic molecules by parallel and combinatorial synthesis and the scavenging of solution-phase reactants or byproducts. 相似文献
992.
An Assay for the Quantitation of Photofrin in Tissues and Fluids 总被引:1,自引:0,他引:1
David A. Bellnier William R. Greco John C. Parsons Allan R. Oseroff Alex Kuebler Thomas J. Dougherty 《Photochemistry and photobiology》1997,66(2):237-244
A method for determining the concentration of Photofrin in tissues and biological fluids was developed. The procedure is based on the dissolution of biological material with Solvable a commercially available tissue so-lubilizer, followed by porphyrin-specific fluorescence detection and measurement. It was found necessary to use a quadratic standard curve for the estimation of unknown Photofrin concentrations. While this method is limited to compounds that are stable in strong base, it has the advantages of being sensitive, rapid and low cost . 相似文献
993.
J. Lawry A. Ray D. Klimesch P. Thomas J.-P. Guerbois J. Harrison 《Journal of Thermal Analysis and Calorimetry》2005,80(3):637-641
Summary Due to growing environmental concerns and the need to use less energy-intensive building products, alternatives and improvements to Portland cement (PC) are being actively researched worldwide. Use of supplementary materials is now a common practice where PC is the predominant component of inorganic building products. This study aims to investigate the potential of magnesia (MgO), derived from a naturally occurring raw material magnesite, as a supplementary material. Results from mortar samples prepared with 10 and 20% replacements of ordinary Portland cement (OPC) by MgO are presented. DTA-TG was used to study and characterise the hydration behaviour of MgO in OPC environment after 3, 7, 14, 28, 56 and 90 days of moist curing. Microstructural and compressive strength determinations providing additional information on the influence of hydrated phases are also reported. 相似文献
994.
In contrast to the histone-modifying action of other complexes of the type CpML(n)R, the compound obtained by linking the phenyl rings of two CpW(CO)(3)Ph moieties to the DNA-binding agent spermine selectively cleaves DNA in DNA-histone assemblies. 相似文献
995.
Detection of phosphoproteins on electroblot membranes using a small-molecule organic fluorophore 总被引:1,自引:0,他引:1
A new formulation of the small-molecule organic fluorophore, Pro-Q Diamond dye, has been developed that permits rapid and simple detection of phosphoproteins directly on polyvinylidene difluoride (PVDF) or nitrocellulose membranes (electroblots). Protein samples are first separated by electrophoresis and then electroblotted to membranes, stained and destained, in an analogous manner as typically performed with Amido Black or Ponceau S dye staining of total protein profiles. After staining, blots are imaged using any of a variety of laser-based gel scanners, xenon-arc lamp-based gel scanners or charge-coupled device (CCD) camera-based imaging devices equipped with UV trans- or epi-illumination. The uncomplicated and reliable staining protocol delivers results in as little as 1 h and the limit of detection for the stain is typically 2-4 ng of phosphoprotein with a linear dynamic range of approximately 15-fold. Compared with traditional radiolabeling and antibody-based approaches, the new method offers significant advantages, including avoidance of radioactivity, no need for expensive antibodies, no requirement for blocking unoccupied sites on the membrane with protein or detergent solutions, no sequence context-specific binding to phosphorylated amino acid residues and the ability to analyze the native, steady-state phosphorylation of proteins obtained directly from tissue specimens or body fluids. Pro-Q Diamond dye binds directly and exclusively to the phosphate moiety, allowing it to detect the broadest spectrum of phosphorylated proteins possible. The stain binds noncovalently to phosphoproteins and is thus fully compatible with matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) or Edman sequencing. The blot stain is also compatible with standard colorimetric, fluorogenic, and chemiluminescent detection techniques employed in immunoblotting. 相似文献
996.
Shultz DA Vostrikova KE Bodnar SH Koo HJ Whangbo MH Kirk ML Depperman EC Kampf JW 《Journal of the American Chemical Society》2003,125(6):1607-1617
We report molecular structures and temperature-dependent magnetic susceptibility data for several new metal complexes of heterospin triplet ground-state biradical ligands. The ligands are comprised of both nitronyl-nitroxide (NN) and semiquinone (SQ) spin carriers. Five compounds are five-coordinate M(II) complexes (M = Mn, Co, Ni, Cu, and Zn), and one is a six-coordinate Ni(II) complex. Five compounds were structurally characterized. During copper complex formation a reaction with methanol occurs to form a unique methoxy-substituted SQ ring. Variable-temperature magnetic susceptibility studies are consistent with strong intraligand (NN-SQ and NN-PhSQ) ferromagnetic exchange coupling. For the five-coordinate Mn, Co, and Ni complexes, the S = 1 ligand is antiferromagnetically coupled to the metal. For both the five-coordinate Cu complex and the six-coordinate Ni complex, the ligand is ferromagnetically coupled to the metal spins in accordance with orbital symmetry arguments. Despite the low molecular symmetries, the predicted trend in metal-ligand exchange interactions is supported by spin dimer analysis based on extended Hückel calculations. For (NN-SQ)NiTp(Cum,Me)() (Tp(Cum,Me)() = hydro-tris(3-cumenyl-5-methylpyrazolyl)borate), an antisymmetric exchange term was required for the best fit of the magnetic susceptibility data. Antisymmetric exchange was less important for the other complexes due to inherently smaller Deltag. Finally, it is shown that intraligand exchange coupling is of paramount importance in stabilizing high-spin states of mixed metal-biradical complexes. 相似文献
997.
Natural Occurrence of C(15)-Epimeric Coleons C and D and its Significance to the Stereochemistry of the Formation of a Spirocyclopropanring In a previous paper some evidence was presented for a predominant occurrence of epimeric coleons ((15S)-coleon C ((15 S)- 1a ), and (15S)-coleon D ((15S)- 2a )) in Plectranthus lanuginosus [1], The proposed structures have now been proven by careful comparison of their physical data with those of the already described C(15)-epimers whose structures were deduced by X-ray analysis of a derived cis-diketone 3 [5], Examination of the epimeric purity of coleons possessing a 2-hydroxy-1-methylethyl side-chain (coleons C , D , H , I , I ′ and derivatives) isolated from seven different species (Coleus, Plectranthus and Solenostemon) has shown that these coleons always occur as a mixture of C(15)-epimers, although in most cases with one predominant epimer. The consequences for the stereochemistry of the postulated in vivo formation of the methyl-substituted spirocyclopropane substructure is discussed. 相似文献
998.
Stationary phase containing quinolin-8-ol immobilized on macroporous methacrylate support for the affinity chromatography of porcine pepsin A is described. Optimized chromatographic conditions for separation of porcine pepsin A on this stationary phase were found investigating the influence of pH, concentration, ionic strength and chemical composition of the used mobile phases. The stationary phase shows a good reproducibility of chromatographic analyses (relative standard deviation, +/-2%), a high recovery (ca. 93%) and a satisfactory capacity (13 mg pepsin A/1 mL stationary phase) for porcine pepsin A. The obtained findings confirm the applicability of affinity chromatography on the stationary phase with immobilized quinolin-8-ol to the isolation and determination of porcine pepsin A. 相似文献
999.
Griesbeck AG Heinrich T Oelgemöller M Lex J Molis A 《Journal of the American Chemical Society》2002,124(37):10972-10973
An elaborated protocol is described which allows the efficient transformation of di-, tri-, and tetrapeptides into cyclopeptides with a minimum of protection and activation chemistry using the photoinduced electron transfer initiated decarboxylation of N-phthaloyl peptides resulting in C-C coupling between the initially formed carbon radicals. 相似文献
1000.
Thomas Garoff Solveig JohanssonKari Pesonen Päivi WaldvogelDaniel Lindgren 《European Polymer Journal》2002,38(1):121-132
In this study we prepared seven different Ziegler-Natta catalysts and polymerised them at different hydrogen concentrations in order to investigate their kinetic behaviour during polymerisation. The objective was to see whether the results corresponded to what could be expected on the basis of Kissin's β-agostic deactivation theory. According to this theory, hydrogen causes the formation of dormant sites due to the formation of β-agostic coordination from the ethyl groups formed after hydrogen termination. According to this theory, the more hydrogen that is used, the more β-agostic coupling and the smaller percentage of Ti in a polymerising state. This β-agostic coupling would thus explain the lower activity level seen in polymerisation where more hydrogen has been used.The results of this study showed that none of the catalysts showed the kind of behaviour that would correspond to what could be predicted on the basis of Kissin's theory. Deactivation could be detected only when a lower amount of hydrogen was used. When higher amounts of hydrogen were used in polymerisation there was a clear delay in activation time of the catalysts. This particularly seemed to be the case for catalysts where Ti was present as Ti(IV). This delay in the activation of the catalyst caused a decrease in activity in addition to the normal decrease in activity due to hydrogen replacing C2′′ in the polymerisation process.The only catalyst showing no delay in activation was a silica-based PE ZN catalyst where the Ti was already in trivalent form. In this case no decrease in activity was observed in addition to the normal decrease in activity caused by hydrogen replacing C2′′ in the polymerisation process. 相似文献