Micellar catalysis of the reaction of 2,4-dinitrofluorobenzene with phenoxide and thiophenoxide ions

The reactions of 2,4-dinitrofluorobenzene with phenoxide and thiophenoxide ion in water are strongly catalyzed by micelles of cetyltrimethylammonium bromide (CTABr) by factors of 230 and 1100 respectively. Nonionic micelles of Brij weakly catalyze the reaction with thiophenoxide ion. Spectral measurements show that phenoxide, and especially thiophenoxide, ions interact strongly with micelles of CTABr which also markedly change the acid dissociation of phenol under given buffer conditions.     

The applicability of DTA and DSC techniques to the study of the kinetics of phase transition reactions

Differential thermal analysis and differential scanning calorimetry techniques have been used to study the kinetics of phase transitions. The aragonite/calcite transformation was chosen as test reaction.Marked discrepancies were observed between the DTA kinetic results and those obtained from isothermal kinetic measurements. This disagreement is associated with the difficulty of determining accurately the reaction rate of the process from a DTA curve.In contrast, in DSC measurements, where the reaction rate is given by the height of the peak from the base-line, it is possible to get a satisfactory fit of the data, and the kinetic results obtained with this technique are in good agreement with the isothermal ones.

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Zusammenfassung Die Differentialthermoanalyse und DSC wurden zur Untersuchung der Kinetik von Phasenübergängen eingesetzt. Die Umwandlung Aragonit/Calcit wurde als Testreaktion gewählt.Bedeutende Diskrepanzen wurden zwischen den kinetischen Ergebnissen der DTA und den durch isotherme kinetische Messungen erhaltenen Ergebnissen beobachtet. Diese Abweichungen sind damit verbunden, daß es schwierig ist, die Reaktionsgeschwindigkeit des Vorgangs aus einer DTA-Kurve genau zu ermitteln.Bei DSC-Messungen,wo die Reaktionsgeschwindigkeit durch die Höhe des Peaks von der Grundlinie gegeben ist, kann eine befriedigende Anpassung der Daten erhalten werden, und die durch diese Technik erhaltenen kinetischen Ergebnisse sind in guter Übereinstimmung mit den isothermen Ergebnissen.

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Engineering reactions in crystalline solids: predicting photochemical decarbonylation from calculated thermochemical parameters

A detailed thermochemical analysis of the alpha-cleavage and decarbonylation reactions of acetone and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a very important role on the thermodynamics of the alpha-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical alpha-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.     

Electrically actuated, pressure-driven microfluidic pumps

In order to make the lab-on-a-chip concept a reality, it is desirable to have an integrated component capable of pumping fluids through microchannels. We have developed novel, electrically actuated micropumps and have integrated them with microfluidic systems. These devices utilize the build-up of electrolysis gases to achieve pressure-driven pumping, only require small voltages (approximately 10 V), and have approximate dimensions of 5 cm x 3 cm x 2 cm. Furthermore, these micropumps are composed of relatively inexpensive materials, and the reversible sealability of their poly(dimethylsiloxane) body to different microfluidic arrays enables repeated uses of the same pump. Under an applied potential of 10 V, three different micropumps had average flow rates of 8-13 microL min(-1) for water being pumped through five different 2 cm-long, 5500 microm(2) cross-sectional-area channels in poly(methyl methacrylate), in approximate agreement with predicted pump rates. We have also evaluated pump operation at the lower applied potential of 8 V and observed an average flow rate of 6.1 microL min(-1) for a pump-channel system. The current micropump design is capable of sustaining pumping pressures in the range of 300 kPa. The various advantages of these micropumps make them well suited for use in lab-on-a-chip analysis techniques.     

Global bifurcations in a laser with injected signal: Beyond Adler's approximation

We discuss the dynamics in the laser with an injected signal from a perturbative point of view showing how different aspects of the dynamics get their definitive character at different orders in the perturbation scheme. At the lowest order Adler's equation [Proc. IRE 34, 351 (1946)] is recovered. More features emerge at first order including some bifurcations sets and the global reinjection conjectured in Physica D 109, 293 (1997). The type of codimension-2 bifurcations present can only be resolved at second order. We show that of the two averaging approximations proposed [Opt. Commun. 111, 173 (1994); Quantum Semiclassic. Opt. 9, 797 (1997); Quantum Semiclassic. Opt. 8, 805 (1996)] differing in the second order terms, only one is accurate to the order required, hence, solving the apparent contradiction among these results. We also show in numerical studies how a homoclinic orbit of the Sil'nikov type, bifurcates into a homoclinic tangency of a periodic orbit of vanishing amplitude. The local vector field at the transition point contains a Hopf-saddle-node singularity, which becomes degenerate and changes type. The overall global bifurcation is of codimension-3. The parameter governing this transition is theta, the cavity detuning (with respect to the atomic frequency) of the laser. (c) 2001 American Institute of Physics.     

Dual-purpose gas chromatographic injection device for pressurized liquid and gas injection

A dual-purpose gas chromatographic injection device, capable of injecting pressurized liquid sample of up to 5000 psig and gas sample with a volume as high as 5000 μL, has been successfully developed and implemented. The injection device is synergized by the effectiveness of a classical flash vaporization of a syringe injection and the reliability of a proven rotary valve. Depending on the matrix involved, this injection device employs either a commercially available four-port internal valve for liquid sampling or a six-port external valve for gas sampling, a modified removable needle used in standard liquid syringe, and an auxiliary flow stream that can be either mechanical or electronic flow controlled for solute transfer. For pressurized liquid, the device was found suitable of up to nC₁₆ hydrocarbon with no observable carry-over despite the injection device was operating at ambient temperature. A relative standard deviation of less than 2% (n = 20) was obtained for hydrocarbon compounds ranging from nC₈ to nC₁₆. For gas injection, the device performed well even under difficult chromatographic conditions such as with a low column inlet pressure of less than 1 psig. A relative standard deviation of less than 0.5% (n = 10) was obtained for reactive sulfur compounds such as alkyl mercaptans. The device can be operated manually or automated with pneumatic or electrical actuator, is platform neutral, and can be moved amongst instruments without hardware modification as well as implemented for on-line or in situ applications. In this paper, the utility of the device was also demonstrated with selected GC applications of industrial significance.     

Tensor Decomposition With Generalized Lasso Penalties

We present an approach for penalized tensor decomposition (PTD) that estimates smoothly varying latent factors in multiway data. This generalizes existing work on sparse tensor decomposition and penalized matrix decompositions, in a manner parallel to the generalized lasso for regression and smoothing problems. Our approach presents many nontrivial challenges at the intersection of modeling and computation, which are studied in detail. An efficient coordinate-wise optimization algorithm for PTD is presented, and its convergence properties are characterized. The method is applied both to simulated data and real data on flu hospitalizations in Texas and motion-capture data from video cameras. These results show that our penalized tensor decomposition can offer major improvements on existing methods for analyzing multiway data that exhibit smooth spatial or temporal features.     

The International Atomic Energy Agency's program on analytical quality control

For more than thirty years the International Atomic Energy Agency has been assisting laboratories in Member States in maintaining and improving the reliability, i.e. the quality of analyses of nuclear, industrial, environmental and biological materials, and materials of marine origin. Through the Analytical Quality Control Services (AQCS) the Agency initiates and supports improvements in the accuracy of analytical chemical and radiometric measurements and their traceability to basic standards. This is achieved by organizing worldwide and regional intercomparison exercises and by distributing reference materials. The latest biological and environmental reference and intercomparison materials are presented and general information is given on the preparation of materials, intercomparison runs, and the evaluation of reference data. Means to improve the quality of intercomparison results are presented and discussed.     

A remarkable enhancement of the rate of ester thiolysis by synthetic amphiphile vesicles

Cationic surfactant vesicles accelerate the rate of thiolysis of p-nitrophenyl octanoate by n- heptylmercaptan by several million fold in the pH range from 4 to 6, providing an efficient system for ester thiolysis in aqueous solution that is functional even at pH4, i.e. more than 6 pH units below the pKa of the SH group. Analysis of the data in terms of an ion exchange formalism implies that this rate acceleration is due primarily to concentration of the reagents in the dimensionally-restrited environment provided by the vesicle, coupled with small contributions from enhanced dissociation and reactivity of the nucleophile at the vesicle surface(s).