Confinement-induced entropic recoil of single DNA molecules in a nanofluidic structure

The behavior of DNA molecules is observed in a nanofluidic device near the interface of two regions that produce different configuration entropies. An electric field is applied to drive the molecules partway across the interface. Upon removal of the field, the molecules recoil to the higher-entropy region with a profile characteristic of a force localized to the interface and independent of length. This is consistent with a confinement-mediated entropic force, distinct from the well-known entropic elasticity common to all polymers. An estimate of the hydrodynamic drag is used to produce a lower bound for the force. The phenomenon can be exploited to separate long-strand polyelectrolytes according to length.     

A reexamination of forward masking in the auditory nerve

Forward masking, as measured behaviorally, is defined as an increase in a signal's detection threshold resulting from a preceding masker. Previously, forward masking in the auditory nerve has been measured as a reduction in the neural response to a signal when preceded by a masker. However, detection threshold depends on both the magnitude of the response to the signal and the variance of the response. Thus changes in detectability cannot be inferred from response reduction alone. Relkin and Pelli (1987) have described a two-interval forced-choice procedure that may be used to measure the threshold for the detection of a probe signal in recordings of spike counts in single auditory neurons. These methods have been used to study the forward masking of characteristic frequency probe tones by characteristic frequency maskers as masker intensity was varied. Although the masker does reduce the detectability of the probe tone, it was found that the threshold shifts are much less than those observed behaviorally, particularly for intense maskers. In part, the small threshold shifts can be attributed to the reduction in response variance following the masker, which is the result of the adaptation of spontaneous activity. These results imply that behavioral forward masking must result from suboptimal processing of spike counts from auditory neurons at a location central to the auditory nerve.     

Reactions of the iso-butyl radical during 1,1′-azoisobutane pyrolysis

Quantitative analysis of the products formed in 1,1′-azoisobutane pyrolyses in the temperature range of 553°–602°K has shown that the major reactions of the iso-butyl radical are Analysis of initial rate data gave log₁₀k₄/(k_c)^1/2(cm^?3/2.mol ^1/2.sec^?1/2) = 7.54±0.44 ? (136.5 + 4.8) kJ/mol/2.303RT, the Arrhenius parameters obtained being in good agreement with thermodynamic data for reaction (4). Measured values of k_a/(k_c)^1/2 where k_a is the rate constant of the reaction iC₄H₉ + AIB → iC₄H₁₀ +. AIB were consistent with published parameters determined by photolysis of 1,1′-azoisobutane. Combination of photolysis and pyrolysis data gave log₁₀ k_a/(k_c)^1/2(cm^3/2.mol^?1/22.sec^?1/2) = 3.68 ± 0.15 ? (27.2 ± 1.2) kJ/mol/2.303RT. The crosscombination ratio for methyl and iso-butyl radicals has been found to be 0.25, indicating that the geometric mean rule does not hold for methyl and iso-butyl radicals.     

Interaction of cobalt(II) and nickel(II) with a gamma-linked, bis-beta-diketone ligand to yield an unusual coordination motif

Discrete cobalt(II) and nickel(II) complexes of type ML (where L is a bis(2,4-pentanedionate) derivative incorporating a -SCH2CH2S- bridge between the gamma-carbons of respective beta-diketone units) have been synthesised and represent the first examples in which a gamma-substituted, thioether-containing beta-diketone ligand coordinates via a sulfur and oxygen donor in preference to the classical coordination mode involving both beta-diketonate oxygens.     

Microwave-assisted sequential amide bond formation and intramolecular amidation: a rapid entry to functionalized oxindoles

A general method has been developed for the synthesis of N-substituted oxindoles. The two-step process involves initial microwave-assisted amide bond formation between 2-halo-arylacetic acids and various alkylamines and anilines, followed by a palladium-catalyzed intramolecular amidation under aqueous conditions. In the case of alkylamines, the procedure can be carried out as a one-pot process without isolation of the intermediate amide. [structure: see text]