Dynamics of alkyl ammonium intercalants within organically modified montmorillonite: Dielectric relaxation and ionic conductivity

The low-frequency (0.01 Hz-10 MHz) dynamic characteristics of alkyl quaternary ammonium exchanged montmorillonite (SC20A) were investigated to determine the correlation between temperature-dependent changes in the interlayer structure and collective mobility of the surfactant. From 25 to 165 degrees C, SC20A exhibits two interlayer transitions, one ascribed to the melting of the intercalated alkyl chains of the surfactant (20-40 degrees C) and another associated with an abrupt decrease in the interlayer's coefficient of thermal expansion (100 degrees C). For this temperature range, the excess surfactant and residual electrolytes present in commercially manufactured SC20A enhance the direct current conductivity and increase low-frequency space-charge polarization, which is believed to occur across percolation paths established by the surfaces of the SC20A crystallites. In contrast, a higher-frequency relaxation, which was less sensitive to process history and impurity content, is ascribed to relaxation within the interlayer at the surfactant-aluminosilicate interface electrostatic couple. The temperature dependence of these dielectric relaxations indicated a drastic increase in mobility as the interlayer organic phase transitions from static and glasslike into molten and mobile. Overall, SC20A displayed features of alternating current universality, including time-temperature superposition, common in other types of disordered ion-conducting media. The presence of long-range transport and its sensitivity to low amounts of impurities imply that from a dynamic perspective the local environment of the surfactants are substantially diverse and a minority fraction, such as at the edge of the crystallite (gallery and aluminosilicate layer), may dominate the lower-frequency dielectric response.     

Converse theorems assuming a partial euler product

Associated to a newform f(z) is a Dirichlet series L _f (s) with functional equation and Euler product. Hecke showed that if the Dirichlet series F(s) has a functional equation of a particular form, then F(s)=L _f (s) for some holomorphic newform f(z) on Γ(1). Weil extended this result to Γ₀(N) under an assumption on the twists of F(s) by Dirichlet characters. Conrey and Farmer extended Hecke’s result for certain small N, assuming that the local factors in the Euler product of F(s) were of a special form. We make the same assumption on the Euler product and describe an approach to the converse theorem using certain additional assumptions. Some of the assumptions may be related to second order modular forms. This work resulted from an REU at Bucknell University and the American Institute of Mathematics. Research supported by the American Institute of Mathematics and the National Science Foundation.     

(Thiocarbonyl‐α‐thio)carboxylic acid derivatives as transfer agents in reversible addition–fragmentation chain‐transfer polymerizations

Ethyl S‐(thiobenzoyl)thioacetate, ethyl S‐thiobenzoyl‐2‐thiopropionate, and S‐(thiobenzoyl)thioglycolic acid were used as chain‐transfer agents for the reversible addition–fragmentation chain‐transfer (RAFT) polymerizations of styrene, methyl methacrylate, and butyl acrylate. Of these polymerizations, only those of styrene and butyl acrylate with any of the transfer agents showed molecular weight control corresponding to controlled/living polymerizations. The best molecular weight control was observed for the polymerizations of styrene and butyl acrylate with ethyl (S)‐thiobenzoyl‐2‐thiopropionate. Semiempirical PM3 calculations were performed for the investigation of the relative heats of reaction of the chain‐transfer equilibria between the aforementioned chain‐transfer agents and dimer radicals of the three monomers. The molecular weight control of the polymerizations correlated with the stability trend of the leaving‐group radical of the chain‐transfer agent. This relatively simple computational model offered some value in determining which transfer agents would show the best molecular weight control in RAFT polymerizations. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 555–563, 2002; DOI 10.1002/pola.10143     

Evaluation of the BAX system for detection of Listeria monocytogenes in foods: collaborative study

A multilaboratory study was conducted to compare the automated BAX system and the standard cultural methods for detection of Listeria monocytogenes in foods. Six food types (frankfurters, soft cheese, smoked salmon, raw, ground beef, fresh radishes, and frozen peas) were analyzed by each method. For each food type, 3 inoculation levels were tested: high (average of 2 CFU/g), low (average of 0.2 CFU/g) and uninoculated controls. A total of 25 laboratories representing government and industry participated. Of the 2335 samples analyzed, 1109 were positive by the BAX system and 1115 were positive by the standard method. A Chi square analysis of each of the 6 food types, at the 3 inoculation levels tested, was performed. For all foods, except radishes, the BAX system performed as well as or better than the standard reference methods based on the Chi square results.     

High-temperature electrocatalysis using thermophilic P450 CYP119: dehalogenation of CCl4 to CH4

The use of a thermophilic cytochrome P450, CYP119, in electrocatalytic dehalogenations of C1 halocarbon solvents is studied. Temperature stable enzyme-modified electrodes were constructed using sol-gel and polymeric surfactant approaches. CYP119 deposited in a dimethyldidodecylammonium poly(p-styrene sulfonate) (DDAPSS) film has good retention of electrochemical activity up to 80 degrees C. At potentials approaching the FeII/I couple, the CYP119/DDAPSS films demonstrate high catalytic dehalogenations of the C1 chloromethanes CCl4, CHCl3, and CH2Cl2. Product analysis identified mixtures of sequentially dechlorinated products up to methane; no evidence for radical-coupled products was observed. The yield of methane from the CYP119-catalyzed reduction of CCl4 is increased 35-fold from 25 degrees C to 55 degrees C. In combination with the lack of C2 products, the facility of an overall eight-electron reductive dehalogenation suggests that the substrate is constrained within the protein during electrocatalytic turnover.     

Radiocarbon ages of lacustrine deposits in volcanic sequences of the Lomas Coloradas area, Socorro Island, Mexico

Extensive eruptions of alkalic basalt from low-elevation fissures and vents on the southern flank of the dormant volcano, Cerro Evermann, accompanied the most recent phase of volcanic activity on Socorro Island, and created the Lomas Coloradas, a broad, gently sloping terrain comprising the southern part of the island. We obtained 14C ages of 4690 +/- 270 BP (5000-5700 cal BP) and 5040 +/- 460 BP (5300-6300 cal BP) from lacustrine deposits that occur within volcanic sequences of the lower Lomas Coloradas. Apparently, the sediments accumulated within a topographic depression between two scoria cones shortly after they formed. The lacrustine environment was destroyed when the cones were breached by headward erosion of adjacent stream drainages. This was followed by the eruption of a thin basaltic flow from fissures near the base of the northernmost cone. The flow moved downslope for a short distance and into the drainages that presently bound the study area on the east and west. The flow postdates development of the present drainage system and may be very recent. Our 14C data, along with historical accounts of volcanic activity over the last century, including submarine eruptions that occurred a few km west of Socorro in early 1993, underscore the high risk for explosive volcanism in this region and the need for a detailed volcanic hazards plan and seismic monitoring.     

Large Motions of a Moored Floating Breakwater Modeled as an Impact Oscillator

Two-dimensional motions of a floating breakwater moored to thesea floor by two cables are considered. The breakwater is modeled bothas a point mass and as a rigid body. The mooring lines are assumed tohave no effect on the breakwater when they are slack, and to provide aninstantaneous impulsive force when they become taut, analogous to animpact oscillator or a ball bouncing on a rigid surface. The axialcomponent of the velocity is reduced at this instantaneous tautcondition. Fluid inertia and damping are not included, and the waveforces are assumed to be harmonic. A critical force is defined, and theeffects of the forcing frequency, the coefficient of restitution, andthe shape and size of the body on the critical force are examined.Trajectories of the motion are plotted and the impact velocities arecomputed and analyzed. Knowledge of the number and magnitude of theseimpacts is useful in assessing fatigue of the mooring lines.     

Computer models for masked hearing experiments with beluga whales (Delphinapterus leucas).

Environmental assessments of manmade noise and its effects on marine mammals need to address the question of how noise interferes with animal vocalizations. Seeking the answer with animal experiments is very time consuming, costly, and often infeasible. This article examines the possibility of estimating results with software models. A matched filter, spectrogram cross-correlation, critical band cross-correlation, and a back-propagation neural network detected a beluga vocalization in three types of ocean noise. Performance was compared to masked hearing experiments with a beluga whale [C. Erbe and D. M. Farmer, Deep-Sea Res. II 45, 1373-1388 (1998)]. The artificial neural network simulated the animal data most closely and raised confidence in its ability to predict the interference of a variety of noise source with a variety of vocalizations.