A high sensitivity titration calorimeter using pyroelectric sensor

A new sensitive isothermal titration microcalorimeter using polyvinylidene difluoride (PVDF) as detector has been developed. Heat pulses of less than 0.4 μJ can be detected and the baseline noise level (p-p) is 40 nW. The calorimeter is constructed with one reaction cell (0.7 ml) insulated by several radiation shields inside a vacuum chamber. The performance of the instrument was examined by measuring the heat of protonation of Tris with HCl. The enthalpy of reaction was found to be ?49±1 kJ·mol^?1, in good agreement with the reported value of ?47.5 kJ·mol^?1.     

Surface heating and energy transfer in pulsed microwave catalytic systems: A microwave-induced acoustic study

Since the early demonstrations of our concept of pulsed microwave catalysis in chemistry, we have witnessed the coming of age of the technique as an enabling technology in the industrial world, despite the inadequate understanding of the basic mechanisms of how microwaves interact with metallic surface sites and the subsequent energy transfer. We shall present here some very recent developments of the microwave-induced acoustic technique and its applications to a better understanding of the basic surface heating and energy transfer phenomena in pulsed microwave catalytic systems.     

Resonance ionization spectroscopy for trace analysis and fundamental research

Resonance ionization spectroscopy (RIS) and its combination with mass spectrometry (RIMS) have grown to become powerful techniques, which offer high sensitivity as well as elemental and isotopic selectivity. The principles of RIS and RIMS are introduced; they primarily concern the analysis of the optical spectra for the choice of efficient excitation schemes and the suitable design of the experimental apparatus. Recent applications span from studies of short-lived isotopes at on-line mass separators to a wide variety of trace analysis applications for radioactive isotopes, which can range from measurements of solar neutrino flux to environmental assessment.On leave from Pacific Northwest Laboratory, Richland, USA     

Effect of structural variation within cationic azo-surfactant upon photoresponsive function in aqueous solution

The cationic azo-surfactants possessing different spacers and tail alkyl chain lengths have been synthesized by azocoupling ofp-alkylaniline orop-ethoxyaniline with phenol, followed by alkylation and quaternalization with dibromoalkane and trimethylamine, respectively. These surfactants showed a good solubility in water. A reversibletrans-cis isomerization of the azosurfactants by photoirradiation was assessed by UV-Vis absorption spectra. Due to a difference in HLB between thetrans- andcis-surfactants, the observed critical micelle concentration (CMC) values and the electric conductivity of the surfactant solution at above the CMC were significantly affected by the photoinducedtrans-cis isomerization. The azo-surfactants bearing moderate alkyl chain lengths such as surfactants 6 (R₂=C₂H₄, R₃=C₄H₉) and 9 (R₂=C₄H₈, R₃=C₂H₅) were found to be effective to achieve large CMC changes (3.6 mmol/L for 6 and 5.9 mmol/L for 9) by UV-light irradiation. The replacement of the tail chain species also affected the photoresponsive function. The surfactant 12, possessingp-ethoxy group as the tail chain, was found to form a stable micelle aggregation as compared with the structurally related surfactant 10 having ethyl unit as its tail group, but it exhibited a large CMC change (5.3 mmol/L) by UV-light irradiation.     

Large Sample Properties of Mixture Models with Covariates for Competing Risks

We study the large-sample properties of a class of parametric mixture models with covariates for competing risks. The models allow general distributions for the survival times and incorporate the idea of long-term survivors. Asymptotic results are obtained under a commonly assumed independent censoring mechanism and some modest regularity conditions on the survival distributions. The existence, consistency, and asymptotic normality of maximum likelihood estimators for the parameters of the model are rigorously derived under general sufficient conditions. Specific conditions for particular models can be derived from the general conditions for ready check. In addition, a likelihood-ratio statistic is proposed to test various hypotheses of practical interest, and its asymptotic distribution is provided.     

Thermoelectric properties of tin clathrates under hydrostatic pressure

We report the temperature dependence of electrical resistance (R) and thermopower (S) of clathrate Cs₈Sn₄₄ under high pressure up to 1.2 GPa. We observe a reversible gap widening, prominent relaxation effect of R, irreversible increase of |S| under high pressure. We also find that the power factor S²σ (σ: electrical conductivity) reaches a maximum at pressure of 0.3 GPa. Comparison of the experimental results with band structure calculations suggests that the intrinsic vacancy in the clathrate structure of Cs₈Sn₄₄ plays an important role in transport properties under high pressure. Measurements on Cs₈Zn₄Sn₄₂, a clathrate which has defects other than vacancies, are compared with Cs₈Sn₄₄. The results indicate that replacing Sn by Zn has similar effect as the intrinsic vacancy on S.     

An efficient lasing action from pyrromethene 556 dye-doped organically modified silicates

Organically modified solid-state silicates (ORMOSILS) doped with a new laser dye 1,3,5,7,8-pentamethylpyrromethene-2,6-disulfonate-BF₂ complex (pyrromethene 556) have been synthesized by a sol-gel method and the compositional effects on pore characteristics, fluorescence and lasing properties have been investigated. It is found that the use of dimethylsulfoxide and γ-glycidoxypropyltrimethoxysilane could greatly change the structure properties of sol-gel derived ORMOSILS cage, and thus the fluorescence and lasing properties of the materials could improve significantly. A successful laser oscillation from this dye-doped ORMOSILS sample has been achieved upon pumping with a Q-switched frequency-doubled Nd:YAG laser at 532 nm. A slope efficiency of 54% with a useful lifetime greater than 10,000 shots has been demonstrated at a pump repetition rate of 1 Hz and a pump intensity of 1 J/cm² by using the new ORMOSILS cage on our newly designed laser system. Our results have shown that it is possible to obtain a high-efficiency with a long-lifetime for a compact new laser device by low cost dye-doped solid-state ORMOSILS.     

The Minimax Estimation of Solutions of Boundary-Value Problems of Filtration in Multicomponent Schistous Media by Incomplete Data

We consider systems described by boundary-value problems for elliptic second-order partial differential equations with discontinuous coefficients appearing in the study of steady-state processes of filtration of a liquid in multicomponent media under nonhomogeneous conditions of a nonideal contact. Minimax estimates for functionals of solutions of these equations are found by using observations of states of the system. We assume that the right hand sides of equations, boundary conditions, and junction conditions on borders of media as well as errors in measurements are not known precisely, but we know only the sets to which they belong. We prove that the finding of minimax estimates can be reduced to the solving of some systems of integro-differential equations.