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991.
Stephenson KA Banerjee SR Besanger T Sogbein OO Levadala MK McFarlane N Lemon JA Boreham DR Maresca KP Brennan JD Babich JW Zubieta J Valliant JF 《Journal of the American Chemical Society》2004,126(28):8598-8599
A bifunctional ligand that is capable of forming Re and 99mTc complexes as complementary fluorescent and radioactive probes was developed. The tridentate bis(quinoline) amine ligand, which is referred to as the SAACQ system, was prepared in a single step from Fmoc protected lysine in high yield. Reaction of the SAACQ ligand with [Re(CO)3Br3]2- resulted in the formation of the SAACQ-(Re(CO)3)+complex which exhibits favorable fluorescence properties including a long lifetime and a large Stoke's shift. Because the SAACQ ligand is derived from an amino acid, it can readily be linked to or incorporated within peptides as a means of targeting the probe to specific receptors. To demonstrate this feature, the SAACQ ligand and the SAACQ-Re complex were incorporated into fMLFG, a peptide that binds to the formyl peptide receptor (FPR). Uptake of the fMLF[(SAACQ-Re(CO)3)+]G conjugate into human leukocytes in vitro was visualized by fluorescence microscopy, and the observed distribution of the peptide was similar to that of a well-established fluorescent FPR probe. The corresponding Tc complex, fMLF[(SAACQ-99mTc(CO)3)+]G, was prepared in excellent yield from [99mTc(CO)3(OH2)3]+, which affords the opportunity to correlate the results of the microscopy experiments with in vivo radioimaging studies because the probes are isostructural. 相似文献
992.
Karin Briner Bruno Bernet Jean-Luc Maloisel Andrea Vasella 《Helvetica chimica acta》1994,77(7):1969-1984
The regio- and stereoselectivity of the glycosidation of the partially protected mono-alcohols 3 and 7 , the diols 2 and 8 , and the triol 4 by the diazirine 1 have been investigated. Glycosidation of the α-D -diol 2 (Scheme 2) gave regioselectively the 1,3-linked disaccharides 11 and 12 (80%, α-D /β-D 9:1), whereas the analogous reaction with the βD -anomer 8 led to a mixture of the anomeric 1,3- and 1,4-linked disaccharides 13 (12.5%), 14 (16%), 15 (13%), and 16 (20.5%; Table 2). Protonation of the carbene by OH–C(4) of 2 is evidenced by the observation that the α-D -mono-alcohol 3 did not react with 1 under otherwise identical conditions, and that the β-D -alcohol 7 yielded predominantly the β-D -glucoside 18 (52%) besides 14% of 17 . Similarly as for the glycosidation of the diol 2 , the influence of the H-bond of HO? C(4) on the direction of approach of the carbene, the role of HO? C(4) in protonating the carbene, and the stereoelectronic control in the interception of the ensuring oxycarbenium cation are evidenced by the reaction of the triol 4 with 1 (Scheme 3), leading mostly to the α-D -configurated 1,3-linked disaccharide 19 (41%), besides its anomer 20 (16%), and some 4-substituted β-D -glucoside 21 (9%). No 1,6-linked disaccharides could be detected. In agreement with the observed reactivity, the 1H-NMR and IR spectra reveal a strong H-bond between HO? C(3) and the phthalimido group in the α-D -, but not in the β-D -allosides. The different H-bonds in the anomeric phthalimides are in keeping with the results of molecular-mechanics calculations. 相似文献
993.
The charge state-dependent dissociation of various DNA duplexes and drug/duplex complexes has been investigated using collisionally activated dissociation (CAD) in a quadrupole ion trap mass spectrometer (QIT-MS). Several non-self-complementary 14-residue oligonucleotides were employed, in addition to an array of known DNA-interactive ligands, including the intercalators daunomycin and nogalamycin, as well as the minor groove binding agents distamycin, netropsin, 4',6-diamidino-2-phenylindole, and Hoechst 33342. In general, the dissociation pathways exhibited by both the duplexes and the drug/duplex complexes were found to be markedly sensitive to initial charge state. Time- and activation voltage-independent duplex strand separation predominated for higher charge states, which was interpreted to be a result of internal Coulombic repulsion or partial unzipping in the interface, while time- and activation voltage-dependent covalent cleavage predominated for lower charge states. The identity of the drug and the sequence of the duplex were both found to affect the competition between different dissociation processes. The dissociation pathways for the lower charge state complexes are probably more reflective of specific drug-DNA interactions because Coulombic and/or conformational effects are less marked for these precursors. 相似文献
994.
Balss KM Ross D Begley HC Olsen KG Tarlov MJ 《Journal of the American Chemical Society》2004,126(41):13474-13479
Two types of DNA hybridization assays are demonstrated with temperature gradient focusing (TGF) and peptide nucleic acids (PNAs). In TGF, the application of a controlled temperature gradient along the length of a microchannel filled with an appropriate temperature-dependent buffer results in the formation of a gradient in both the electric field and electrophoretic velocity. Ionic species move in this gradient and concentrate at a unique point where the total velocity sums to zero. The first assay is a mixing assay in which PNA is allowed to flow through spatially focused DNA targets within a capillary. The second assay detects single base pair mutations (SBPM) by monitoring the fluorescence intensity of PNA/DNA duplexes as a function of temperature within the capillary. The SBPM analysis can be performed in less than 5 min with 100-fold more dilute analyte compared to conventional UV melting measurements. 相似文献
995.
Peter Olsén Karin Odelius Ann‐Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3039-3045
Main‐chain‐functionalized poly(L ‐lactide) (PLLA) with pendant unsaturations was synthesized through a one‐pot postpolymerization procedure with the PLLA homopolymer as the starting material. The material was functionalized through α‐hydrogen abstraction by a sterically hindered strong base, lithium diisopropylamide, followed by the addition of an acid chloride. Two different acid chlorides were examined, lauroyl chloride as a concept electrophile and oleoyl chloride to provide the pendant unsaturations. The semisolvated system, together with branching reactions from the alpha position of the acid chloride, yielded a high molar amount of the incorporated reactant in the material. The unsaturations were preserved under the chosen conditions and the material exhibited surfactant‐like properties in blends with oleic acid and PLLA. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
996.
997.
Lotta T. Tegler Guillaume Nonglaton Frank Büttner Karin Caldwell Tony Christopeit U. Helena Danielson Karin Fromell Thomas Gossas Anders Larsson Paola Longati Thomas Norberg Ramesh Ramapanicker Johan Rydberg Lars Baltzer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2011,123(8):1863-1867
998.
Aleš Doliška Simona Strnad Volker Ribitsch Karin Stana Kleinschek Stefan Willför Bodo Saake 《Cellulose (London, England)》2009,16(6):1089-1097
The aim of this study was to setup a method for detection and quantification of monosaccharide components in technical galactoglucomannas
(T-GGM) from spruce wood using capillary zone electrophoresis (CZE). CZE technique was optimised regarding borate buffer concentrations,
EOF modifier application, and system pH. Aqueous solution of T-GGM was chemically hydrolysed by sulphuric acid, in an autoclave.
In this way obtained monosaccharides were derivatized with 4-amino benzoic acid ethyl ester via reductive amination using
sodium cyanoborohydride. The results of the optimisation procedure showed that the borate buffers at lowest concentrations
(100 and 200 mM) with acetonitrile addition as EOF modifier gave the optimal measurement results, as it showed sufficient
separation at relatively short migration times. The amounts of single monosaccharide components in the T-GGM samples obtained
by the optimised CZE procedure were practically the same in comparison to the results of the well established HPLC-anion exchange
chromatography. On the basis of this research, it was concluded that the capillary zone electrophoresis is an efficient analytical
procedure for the characterisation of galactoglucomannans derived from softwoods. 相似文献
999.
1000.