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51.
Toward a microchip-based solid-phase extraction method for isolation of nucleic acids 总被引:7,自引:0,他引:7
Wolfe KA Breadmore MC Ferrance JP Power ME Conroy JF Norris PM Landers JP 《Electrophoresis》2002,23(5):727-733
A silica-based solid-phase extraction system suitable for incorporation into a microchip platform (nu-total analytical system; nu-TAS) would find utility in a variety of genetic analysis protocols, including DNA sequencing. The extraction procedure utilized is based on adsorption of the DNA onto bare silica. The procedure involves three steps: (i) DNA adsorption in the presence of a chaotropic salt, (ii) removal of contaminants with an alcohol/water solution, and (iii) elution of the adsorbed DNA in a small volume of buffer suitable for polymerase chain reaction (PCR) amplification. Multiple approaches for incorporation of this protocol into a microchip were examined with regard to extraction efficiency, reproducibility, stability, and the potential to provide PCR-amplifiable DNA. These included packing microchannels with silica beads only, generating a continuous silica network via sol-gel chemistry, and combinations of these. The optimal approach was found to involve immobilizing silica beads packed into the channel using a sol-gel network. This method allowed for successful extraction and elution of nanogram quantities of DNA in less than 25 min, with the DNA obtained in the elution buffer fraction. Evaluation of the eluted DNA indicated that it was of suitable quality for subsequent amplification by PCR. 相似文献
52.
Mikhail?A.?VorotyntsevEmail author Magdalena?Graczyk Anna?Lisowska-Oleksiak Jerome?Goux Claude?Moise 《Journal of Solid State Electrochemistry》2004,8(10):818-827
We have studied for the first time the ability of a conducting polymer film, p(Tc3Py), representing a polypyrrole matrix with covalently attached titanocene dichloride (TcCl2) centers, to serve as an intermediator for the electron charge transport between the electrode and the reaction sites of solute reactants. The standard potential of the first of these electroactive species, ferrocene (Fc), is in the range where the polymer matrix is in its slightly oxidized state so that solute Fc species give a reversible response at the surface of this modified electrode. Another solute reactant, TcCl2, was studied in solutions in which it demonstrates a (quasi)reversible behavior at bare electrode surfaces, THF+TBAPF6 and AN+TEACl. The standard redox potential of this species belongs to the range of the electroactivity of immobilized TcCl2 centers (where the matrix is in its non-conducting state) so that the electron charge has to be transported via stepwise redox reactions between neighboring centers inside the film. The combination, solute reactant+film, results in a greater CV current compared to the response of the film in background solution or of the solute species at the bare electrode surface. This current for THF solution even exceeds the sum of separate currents for the film and the reactant. This finding is attributed to a catalytic effect of solute species as redox intermediators for the transformation of immobilized electroactive centers leading to a greater degree of the film reduction. The presence of solute TcCl2 species results in a much greater stability of immobilized centers (compared to the corresponding reactant-free solution), both in the course of CV with the passage of the range of their response and in experiments with the film holding at the potential within this range. This holding leads to an almost constant current related to the reaction of solute species at the film/solution interface. Our estimate shows that immobilized centers undergo above 10,000 reversible transformations (without an observed tendency to the degradation) to ensure the passage of this current. The conclusion has been drawn that immobilized TcCl2 centers are able to serve as sufficiently stable redox intermediators for the electron charge transport across the film, a prerequisite for the catalytic applications of such films.Abbreviations AN acetonitrile - THF tetrahydrofuran - Cp cyclopentadienyl, C5H5 - Cp cyclopentadienyl radical, C5H4 - Fc ferrocene, Cp2Fe - TcCl2 titanocene=bis(cyclopentadienyl)titanium dichloride, Cp2TiCl2 or its radical CpCpTiCl2 - PPy polypyrrole - Tc3Py titanocene-propyl-pyrrole, Cl2TiCpCp(CH2)3NC4H4 - p(Tc3Py) polymer obtained from Tc3Py - TBAPF6 tetrabuthylammonium hexafluorophosphate - TEACl tetraethylammonium chlorideDedicated to Zbigniew Galus on the occasion of his 70th birthday. 相似文献
53.
Biomimetic tris(4-imidazolyl)carbinol derivatives are prepared from imidazole in a short, high-yielding sequence via sulfonamide 1, which is converted to the 2-silylated carbinol 2 by one-pot, sequential 2-functionalization and then 4(5)-functionalization. Alcohol 2 can be transformed either to the parent carbinol 3 or to a desilylated sulfonamide derivative 4. The tripodal alcohol 3 is a convenient precursor to ethers by solvolysis and to metal complexes, as illustrated by the preparation of a bis-tripod complex with iron(III). 相似文献
54.
Eric A. Voight Jerome F. Daanen Bhadra H. Shelat Daniel J. Plata 《Tetrahedron letters》2010,51(45):5904-5907
Starting from a variety of substituted chroman-4-ones, a highly enantioselective CBS reduction using in situ-generated B-H catalyst gave (S)-chroman-4-ols. Azide inversion and reduction gave crude (R)-chroman-4-amines, which could be purified without chromatography by isolation as the (R)-mandelic or d-tartaric acid salts with good yields and excellent ee. 相似文献
55.
An efficient synthesis of 2-amino-oxazolo[4,5-c]quinoline TRPV1 antagonists is described via a thiourea formation/carbodiimide cyclization sequence. Synthetic route optimization eliminates intermediate isolations and facilitates the rapid preparation of a series of novel pentacyclic TRPV1 antagonists. From this series, compound (S)-4 was identified as a potent and selective ligand for the TRPV1 ion channel. 相似文献
56.
We report the enantioselective synthesis of pseudolaric acid B (1a), a diterpene acid isolated from the bark of Pseudolarix kaempferi Gordon, which displays interesting antifungal, antifertility, and cytotoxic activity against multidrug resistant cell lines. Our synthesis utilizes a highly efficient metal-catalyzed [5 + 2] vinylcyclopropane-alkyne intramolecular cycloaddition to construct the polyhydroazulene core of the natural product. Elaboration to the tricyclic scaffold of the pseudolaric acids was completed with an intramolecular alkoxycarbonyl radical cyclization to form the quaternary center and a highly diastereoselective cerium acetylide addition to a methyl ketone for introduction of the acid side chain. 相似文献
57.
Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation 下载免费PDF全文
Yifan Li Dr. Durga Prasad Hari Maria Victoria Vita Prof. Dr. Jerome Waser 《Angewandte Chemie (International ed. in English)》2016,55(14):4436-4454
Hypervalent iodine compounds are privileged reagents in organic synthesis because of their exceptional reactivity. Among these compounds, cyclic derivatives stand apart because of their enhanced stability. They have been widely used as oxidants, but their potential for functional‐group transfer has only begun to be investigated recently. The use of benziodoxol(on)es for trifluoromethylation (Togni's reagents) is already widely recognized, but other transformations have also attracted strong interest recently. In this Review, the development in the area since 2011 will be presented. After a short summary of synthetic methods to prepare benziodoxol(on)e reagents, their use to construct carbon–heteroatom and carbon–carbon bonds will be presented. In particular, the introduction of alkynes by using ethynylbenziodoxol(on)e (EBX) reagents has been highly successful. Breakthroughs in the introduction of alkoxy, azido, difluoromethyl, and cyano groups will also be described. 相似文献
58.
Stéphanie Etienne C. Becker D. Ruch B. Grignard G. Cartigny C. Detrembleur C. Calberg R. Jerome 《Journal of Thermal Analysis and Calorimetry》2007,87(1):101-104
Silica nanoparticles of various sizes have
been incorporated by melt compounding in a poly(methyl methacrylate) (PMMA)
matrix to enhance its thermal and mechanical properties. In order to improve
nanoparticles dispersion, PMMA grafted particles have been prepared by atom
transfer radical polymerization (ATRP) from well-defined silica nanoparticles.
This strategy was expected to ensure compatibility between both components
of the PMMA nanocomposites. TEM analysis have been performed to evaluate the
nanosilica dispersion whereas modified and non-modified silica/PMMA nanocomposites
thermal stability and mechanical properties have been investigated by both
thermogravimetric and dynamical mechanical analysis. 相似文献
59.
V. W. Stone A. M. Jonas R. Legras P. Dubois R. Jerome 《Journal of polymer science. Part A, Polymer chemistry》1999,37(2):233-244
Strongly asymmetric chlorinated polybutadiene‐b‐polystyrene, [P((CB)x‐b‐(PS)y)] diblock copolymers with increasing x/(x + y) ratios (up to 5.2 mol %) have been synthesized by the selective chlorination of the polybutadiene (PB) block in solution. Chlorination has been performed in anhydrous dichloromethane added with an antioxidant [2,2′‐methylenebis‐(6‐tert‐butyl‐4‐methyl‐phenol)], at −50°C, under a continuous Ar flow and in the dark. Under the optimized experimental conditions, the PB chlorination is not complete, but the PS block is left unmodified. Even in the presence of a large chlorine excess (Cl2/butene unit molar ratio of 2.5), the experimental degree of chlorination of homo PB does not exceed 85%. The chlorinated copolymers have been characterized by 1H‐NMR, IR spectroscopy, size‐exclusion chromatography, and elemental analysis. The chlorinated copolymers have also been studied by DSC and SAXS after annealing at 150°C. Although at this temperature the parent homopolymers are immiscible, no microphase separation has been observed for the block copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 233–244, 1999 相似文献
60.
Chemical reactions and processes often involve chiral, yet racemic, cationic reagents, intermediates or products. To afford instead non racemic or enantiopure compounds, an asymmetric ion pairing of the cations with enantiopure anions can be considered--the counter ions behaving as asymmetric auxiliaries, ligands or reagents. Detailed herein is a short review of our approach towards gaining reliable and predictable control over stereoselective ion pairing phenomena through the synthesis and the use of novel configurationally stable hexacoordinated phosphate anions. 相似文献