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1.
Soft Matter ; 5: 1188-1191, 2009 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-19802354

RESUMEN

This paper describes the phase separation of millimetre-scale spheres based on electrostatic charge. Initially, polymeric (Teflon, T; Nylon-6,6, N) and metallic (gold-coated Nylon-6,6, Au(N)) spheres are uniformly mixed in a two-dimensional (2D) monolayer on a gold-coated plate. Oscillating the plate vertically caused the spheres to charge by contact electrification (tribocharging). Positively charged N and negatively charged T spheres attracted each other more strongly than they attracted the capacitively charged, Au(N) spheres. The T and N spheres formed 2D Coulombic crystals, and these crystals separated from the Au(N) spheres. The extent and rate of separation increased with increasing amplitude of agitation during tribocharging, and with decreasing density of spheres on the surface. At high surface density, the T and N spheres did not separate from the Au(N) spheres. This system models the 2D nucleation of an ionic crystal from a polarizable liquid.

2.
J Am Chem Soc ; 131(25): 8746-7, 2009 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-19499916

RESUMEN

This communication describes a new approach for controlling static charging (contact electrification), and resulting electrical discharging, that occurs when two contacting materials separate. The prevention of contact electrification is an important problem; unwanted adhesion between oppositely charged materials, spark-initiated explosions, and damage to microelectronic circuitry are some of the deleterious effects of static charging. Current strategies for controlling contact electrification rely upon dissipating an accumulated charge by making contacting surfaces conductive and, therefore, can be difficult to implement with electrically insulating materials. Specifically, using our understanding of the ion-transfer mechanism of contact electrification, we patterned glass slides with negatively charging areas (clean glass) and positively charging areas (glass silanized with a cationic siloxane terminated with a quaternary ammonium group). The rate of charge separation due to a steel sphere rolling on the patterned glass surface correlated linearly with the percentage of the glass surface that was silanized; the rate of charge transfer was minimal when 50% of the glass surface area was silanized. Patterned surfaces also prevented electrical discharges between electrically conducting (bare steel) or insulating (acrylate-coated steel) spheres rolling on the glass, because the rate of charging was sufficiently slow to prevent electric fields greater than the dielectric strength of air to develop. This strategy for preventing static charging therefore does not require one of the two contacting surfaces to be electrically conductive. More generally, these results show that our enhanced understanding of the ion-transfer mechanism of contact electrification enables the rational design of chemically tailored surfaces for functional electrets.


Asunto(s)
Vidrio/química , Siloxanos/química , Electricidad Estática , Conductividad Eléctrica , Iones/química , Cinética , Estructura Molecular , Acero/química , Propiedades de Superficie
3.
J Am Chem Soc ; 131(26): 9361-7, 2009 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-19534466

RESUMEN

This paper describes a method for the purification of monoclonal antibodies (rat anti-2,4-dinitrophenyl IgG: IgG(DNP); and mouse antidigoxin IgG: IgG(Dgn)) from ascites fluid. This procedure (for IgG(DNP)) has three steps: (i) precipitation of proteins heavier than immunoglobulins with ammonium sulfate; (ii) formation of cyclic complexes of IgG(DNP) by causing it to bind to synthetic multivalent haptens containing multiple DNP groups; (iii) selective precipitation of these dimers, trimers, and higher oligomers of the target antibody, followed by regeneration of the free antibody. This procedure separates the targeted antibody from a mixture of antibodies, as well as from other proteins and globulins in a biological fluid. This method is applicable to antibodies with a wide range of monovalent binding constants (0.1 microM to 0.1 nM). The multivalent ligands we used (derivatives of DNP and digoxin) isolated IgG(DNP) and IgG(Dgn) from ascites fluid in yields of >80% and with >95% purity. This technique has two advantages over conventional chromatographic methods for purifying antibodies: (i) it is selective for antibodies with two active Fab binding sites (both sites are required to form the cyclic complexes) over antibodies with one or zero active Fab binding sites; (ii) it does not require chromatographic separation. It has the disadvantage that the structure of the hapten must be compatible with the synthesis of bi- and/or trivalent analogues.


Asunto(s)
Anticuerpos Monoclonales/aislamiento & purificación , Digoxina/inmunología , Dinitrobencenos/inmunología , Haptenos/química , Inmunoglobulina G/aislamiento & purificación , Sulfato de Amonio , Animales , Anticuerpos Monoclonales/inmunología , Ascitis/inmunología , Sitios de Unión de Anticuerpos , Precipitación Química , Cromatografía en Gel , Digoxina/química , Dimerización , Dinitrobencenos/química , Haptenos/inmunología , Inmunoglobulina G/inmunología , Ratones , Modelos Moleculares , Ratas
5.
Protein Sci ; 17(8): 1446-55, 2008 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-18451358

RESUMEN

This paper reports that the acetylation of lysine epsilon-NH3(+) groups of alpha-amylase--one of the most important hydrolytic enzymes used in industry--produces highly negatively charged variants that are enzymatically active, thermostable, and more resistant than the wild-type enzyme to irreversible inactivation on exposure to denaturing conditions (e.g., 1 h at 90 degrees C in solutions containing 100-mM sodium dodecyl sulfate). Acetylation also protected the enzyme against irreversible inactivation by the neutral surfactant TRITON X-100 (polyethylene glycol p-(1,1,3,3-tetramethylbutyl)phenyl ether), but not by the cationic surfactant, dodecyltrimethylammonium bromide (DTAB). The increased resistance of acetylated alpha-amylase toward inactivation is attributed to the increased net negative charge of alpha-amylase that resulted from the acetylation of lysine ammonium groups (lysine epsilon-NH3(+) --> epsilon-NHCOCH3). Increases in the net negative charge of proteins can decrease the rate of unfolding by anionic surfactants, and can also decrease the rate of protein aggregation. The acetylation of lysine represents a simple, inexpensive method for stabilizing bacterial alpha-amylase against irreversible inactivation in the presence of the anionic and neutral surfactants that are commonly used in industrial applications.


Asunto(s)
Proteínas Bacterianas/metabolismo , Lisina/metabolismo , alfa-Amilasas/metabolismo , Acetilación , Bacillus/enzimología , Proteínas Bacterianas/química , Rastreo Diferencial de Calorimetría , Dicroismo Circular , Electroforesis Capilar , Estabilidad de Enzimas/efectos de los fármacos , Octoxinol/farmacología , Compuestos de Amonio Cuaternario/farmacología , Dodecil Sulfato de Sodio/farmacología , Espectrometría de Masa por Ionización de Electrospray , alfa-Amilasas/química
7.
Langmuir ; 23(19): 9686-94, 2007 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-17696377

RESUMEN

This paper describes the use of several methods of template stripping (TS) to produce ultraflat films of silver, gold, palladium, and platinum on both rigid and polymeric mechanical supports: a composite of glass and ultraviolet (UV)-curable adhesive (optical adhesive, OA), solder, a composite of poly(dimethyl siloxane) (PDMS) and OA, and bare OA. Silicon supporting its native oxide layer (Si/SiO2) serves as a template for both mechanical template stripping (mTS), in which the metal film is mechanically cleaved from the template, and chemical template stripping (cTS), in which the film-template composite is immersed in a solution of thiols, and the formation of the SAM on the metal film causes the film to separate from the template. Films formed on all supports have lower root-mean-square (rms) roughness (as measured by atomic force microscopy, AFM) than films used as-deposited (AS-DEP) by electron-beam evaporation. Monolayers of n-dodecanethiolate formed by the mTS and cTS methods are effectively indistinguishable by scanning tunneling microscopy (STM); molecularly resolved images could be obtained using both types of surfaces. The metal surfaces, before being cleaved, are completely protected from contact with the atmosphere. This protection allows metal surfaces intended to support SAMs to be prepared in large batch lots, stored, and then used as needed. Template stripping thus eliminates the requirement for evaporation of the film immediately before use and is a significant extension and simplification of the technology of SAMs and other areas of materials science requiring clean metal surfaces.

8.
J Am Chem Soc ; 129(14): 4336-49, 2007 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-17358061

RESUMEN

This paper compares the structural and electrical characteristics of self-assembled monolayers (SAMs) of n-alkanethiolates, SCn (n = 10, 12, 14), on two types of silver substrates: one used as-deposited (AS-DEP) by an electron-beam evaporator, and one prepared using the method of template-stripping. Atomic force microscopy showed that the template-stripped (TS) silver surfaces were smoother and had larger grains than the AS-DEP surfaces, and reflectance-absorbance infrared spectroscopy showed that SAMs formed on TS substrates were more crystalline than SAMs formed on AS-DEP substrates. The range of current densities, J (A/cm2), measured through mercury-drop junctions incorporating a given SAM on AS-DEP silver was, on average, several orders of magnitude larger than the range of J measured through the same SAM on TS silver, and the AS-DEP junctions failed, on average, 3.5 times more often within five current density-voltage (J-V) scans than did TS junctions (depending on the length of the alkyl chains of the molecules in the SAM). The apparent log-normal distribution of J through the TS junctions suggests that, in these cases, it is the variability in the effective thickness of the insulating layer (the distance the electron travels between electrodes) that results in the uncertainty in J. The parameter describing the decay of current density with the thickness of the insulating layer, beta, was either 0.57 A-1 at V = +0.5 V (calculated using the log-mean of the distribution of values of J) or 0.64 A-1 (calculated using the peak of the distribution of values of J) for the TS junctions; the latter is probably the more accurate. The mechanisms of failure of the junctions, and the degree and sources of uncertainty in current density, are discussed with respect to a variety of defects that occur within Hg-drop junctions incorporating SAMs on silver.

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