l,6-Dioxaspiro[4,4]nonane-2,7-dione has been found to react readily with alcohols in the presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU). The 4-oxoheptanedioic acid tether obtained bears (l) a free carboxy group, which enables anchoring to aminoalkylated resins, and (2) a 4-oxobutanoate structural motif, which allows release of the target alcohol by a mild hydrazinium acetate treatment. To demonstrate the applicability of the procedure, nucleosides have been derivatized with this simple difunctional linker arm, anchored to a solid phase and subjected to synthesis and subsequent release of oligonucleotides bearing a base-sensitive biodegradable phosphate protection. 相似文献
In the title compound, C30H48NO3+·Cl−·H2O, the cation acts with a water molecule as a chloride ion receptor. The chloride ion forms three strong intramolecular hydrogen bonds. The water molecule forms both an intramolecular bridge between one phenol H atom and the chloride ion, and an intermolecular link to the aliphatic alcohol O atom. Weak intermolecular C—H...Cl and C—H ...O hydrogen bonds provide additional packing interactions. 相似文献
Structure proof of (—)-myrtenol, 3-cyclopentenyl-1-methanol and 5-norbornene-2-endo-methanol has been obtained from their proton magnetic resonance spectra in carbon tetrachloride containing different added amounts of tris(dipivaloylmethanato)europium. For each alcohol, a 1:1 complex structure with Eu(dpm)3 could be computed, in which the calculated pseudocontact shift effects on all skeleton protons of the ring system were consistent with the observed shift effect values. A considerable contact contribution of opposite sign to that of the pseudocontact part of the effect could be estimated for the methylene protons of the CH2OH group. 相似文献
Miniaturized multiplex immunoassays were studied on individual beads to detect analytes in the same reaction mixture. With this approach hands-on time, cost, and amount of reagents as well as waste produced in the assays were reduced. Particles were categorized according to size for immunoassays of prostate specific antigen (PSA) and acute myocardial infarction (AMI) markers. Additionally, free and dual PSA assays were carried out on a single bead. The analyte concentration was detected directly on the surface of the beads using stable, intrinsically fluorescent europium and terbium chelates, and time-resolved fluorometry. Less than 0.4 ng ml−1 PSA (corresponding to ca. 10 amol) was detected in free, dual and multiplex PSA assays and 0.1 and 2.4 ng ml−1 of myoglobin (Mb) and creatine kinase MB (CK-MB), respectively, were monitored in the multiplex AMI marker assay. The effect of bead size and material on free PSA detection was also investigated. The beads were detected three times under different conditions; in liquid, after drying and after dissociating europium ions from the chelate into the DELFIA® fluorescence enhancement solution. The same detection sensitivity was found for the dissociative and non-dissociative methods indicating that the current labeling technology for the surface detection is comparable to the commercial DELFIA system. 相似文献
Two novel peptide scaffolds, viz. cyclo[(N(alpha)-Alloc)Dpr-beta-Ala-(N(alpha)-Fmoc)Dpr-beta-Ala] (1) and cyclo[(N(alpha)-Alloc)Dpr-alpha-azido-beta-aminopropanoyl-(N(alpha)-Fmoc)Dpr-beta-Ala] (2), composed of orthogonally protected 2,3-diaminopropanoyl (Dpr) and beta-alanyl residues, have been described. Fmoc chemistry on a backbone amide linker derivatized resin has been used for the chain assembly. Selective removal of the 4-methyltrityl (Mtt) and 1-methyl-1-phenylethyl protections (PhiPr) exposes the beta-amino and carboxyl terminus, respectively, and on-resin cyclization then gives the desired orthogonally protected cyclo-beta-tetrapeptides (1 and 2). The alpha-amino groups, bearing the Fmoc and Alloc protections and the azide mask, allow stepwise orthogonal derivatization of these solid-supported cyclo-beta-tetrapeptide cores (1 and 2). This has been demonstrated by attachments of various sugar units [viz., acetyl- or toluoyl-protected carboxymethyl alpha-d-glycopyranosides (13-15) and methyl 6-O-(4-nitrophenoxycarbonyl)-alpha-d-glycopyranosides (22-24)] to obtain diverse di- and trivalent glycoclusters (33-42). Acidolytic release (TFA) from the support, followed by conventional NaOMe-catalyzed transesterification (33-40) or hydrazine-induced acyl substitution in DMF (41 and 42), gives the fully deprotected clusters (43-52) as final products. 相似文献
The ultimate nature of streptavidin to bind biotin tightly is widely utilized in many solid-phase based applications to provide a universal binding surface for biotinylated molecules. However, the preparation of the streptavidin coatings by passive adsorption may heavily alter the binding properties of native streptavidin and may not result in the best possible capture surface for demanding solid-phase assays. By introducing sulphydryl groups through primary amines in the protein, we have activated and conjugated native streptavidin into larger protein polymers resulting in high local binding density when coated on polystyrene. This thiolated streptavidin formed through chemical modification has improved adsorption properties and biotin binding capability, compared to the native streptavidin. When this thiolated streptavidin is coated on polystyrene, a dense surface is formed, which provides up to 3-fold increase in the biotin binding efficiency and improves the surface stability by minimizing the desorption of the adsorbed protein from the surface during incubation. Furthermore, this high-capacity surface is resistant to harsh chemical treatments, such as denaturing conditions or mild reducing conditions. The improved adsorption properties of the thiolated streptavidin allow the coating process to be performed with shorter incubation times (15 min), still providing enhanced solid-phase properties, compared to a reference streptavidin surface. 相似文献
A novel selective leaching method for the porogenization of the biodegradable scaffolds was developed. Continuous, predetermined pore structure was prepared by dissolving fast eroding poly(ε‐caprolactone)‐based poly(ester‐anhydride) fibers from the photo‐crosslinked poly(ε‐caprolactone) matrix. The porogen fibers dissolved in the phosphate buffer (pH 7.4, 37 °C) within a week, resulting in the porosity that replicated exactly the single fiber dimensions and the overall arrangement of the fibers. The amount of the porosity, estimated with micro‐CT, corresponded with the initial amount of the fibers. The potential to include bioactive agents in the porogen fibers was demonstrated with the bioactive glass.
We search for B+/--->[K(-/+)pi(+/-)](D)K+/- decays, where [K(-/+)pi(+/-)](D) indicates that the K-/+pi(+/-) pair originates from the decay of a D0 or D (0). Results are based on 120x10(6) Upsilon(4S)-->BB decays collected with the BABAR detector at SLAC. We set an upper limit on the ratio R(Kpi) identical with[Gamma(B+-->[K(-)pi(+)](D)K+)+Gamma(B--->[K(+)pi(-)](D)K-)][Gamma(B+-->[K(+)pi(-)](D) / K+)+Gamma(B--->[K(-)pi(+)](D)K-)]<0.026 (90% C.L.). This constrains the amplitude ratio r(B) identical with|A(B--->D 0K-)/A(B--->D0K-)|<0.22 (90% C.L.), consistent with expectations. The small value of r(B) favored by our analysis suggests that the determination of the Cabibbo-Kobayashi-Maskawa phase gamma from B-->DK will be difficult. 相似文献