Time-resolved intraband electronic relaxation dynamics of Hg(n) (-) clusters (n=7-13,15,18) excited at 1.0 eV

Time-resolved photoelectron imaging has been used to study the relaxation dynamics of small Hg(n) (-) clusters (n=7-13,15,18) following intraband electronic excitation at 1250 nm (1.0 eV). This study furthers our previous investigation of single electron, intraband relaxation dynamics in Hg(n) (-) clusters at 790 nm by exploring the dynamics of smaller clusters (n=7-10), as well as those of larger clusters (n=11-13,15,18) at a lower excitation energy. We measure relaxation time scales of 2-9 ps, two to three times faster than seen previously after 790 nm excitation of Hg(n) (-), n=11-18. These results, along with size-dependent trends in the absorption cross-section and photoelectron angular distribution anisotropy, suggest significant evolution of the cluster anion electronic structure in the size range studied here. Furthermore, the smallest clusters studied here exhibit 35-45 cm(-1) oscillations in pump-probe signal at earliest temporal delays that are interpreted as early coherent nuclear motion on the excited potential energy surfaces of these clusters. Evidence for evaporation of one or two Hg atoms is seen on a time scale of tens of picoseconds.     

Multielement Analysis of Whole Blood Using a Capacitively Coupled Microwave Plasma Atomic Emission Spectrometer

A capacitively coupled microwave plasma atomic emission spectrometer (CMP-AES) has been evaluated as a means for the direct analysis of several of the primary and trace elements in whole blood. A tungsten filament spiral electrode was used with the CMP, and whole blood samples were deposited on the electrode and subsequently dried, ashed, and atomized. The emission was measured with a spectrometer and a charge-coupled-device detector. A sample size of only 2 μl was required and the time for each sample run was under 4 min. This method has a wide dynamic range, allowing the determination of both the primary elements in blood and elements present in trace quantities. Potassium, sodium, lithium, magnesium, manganese, and zinc were studied. Good linearity was observed and the concentration levels obtained for these elements were consistent with literature values. The primary advantages of this method are that no sample pretreatment or dilution is required, the instrument cost is low, and the method is capable of simultaneous multielement analysis on small, discrete samples.     

Sesquiterpenoids and flavonoids from the aerial parts of Tithonia diversifolia and their cytotoxic activity

Cytotoxicity-guided fractionation of the 80% EtOH extract of Tithonia diversifolia has resulted in the isolation of twelve sesquiterpenoids (1-12), including three new ones (4, 10, 12), and three known flavonoids (13-15). The structures of the new compounds were determined by analysis of their spectroscopic data. The isolated compounds showed cytotoxic activity against HL-60 leukemia cells with IC(50) values ranging from 0.13 to 13.0 microM, when etoposide used as a positive control gave an IC(50) value of 0.43 microM. The cancer growth inhibitory property of 9, the main cytotoxic compound in T. diversifolia, was examined using a disease-oriented panel composed of 39 human cancer cell lines in the Japanese Foundation for Cancer Research.     

Electrospray mass spectrometry of methanol and water solutions suppression of electric discharge with SF6 gas

An equation by D. P. H. Smith predicts the capillary voltage required for the onset of electrospray (ES). For different solvents the voltage increases with the square root of the surface tension. Water requires a potential that is 1.8 times higher than that for methanol. This is verified experimentally. The higher potential required for water leads to ES in the presence of corona electric discharge. For low total ES plus corona currents, the electrosprayed analyte ion intensity is not adversely affected by the presence of discharge. At high total currents, there is a large decrease of analyte sensitivity. The sensitivity decrease is probably due to adverse space charge effect at high currents. The discharge can be suppressed by adding sulfur hexafluoride to the ambient gas. Both sensitivity and signal stability are improved. However, the sensitivity still remains lower by a factor of ≈ 4 relative to that observed with methanol. This is attributed to lower efficiency of gas-phase ion formation from charged water, relative to methanol, droplets.     

Bench Scale Studies of the Soil Aeration Process for Bioremediation of Petroleum Hydrocarbons

An alternative to traditional hydrocarbon bioremediation is to pump air through unsaturated soils to create aerobic conditions and induce biodegradation. This study examines the effects of moisture and nutrient augmentation on biodegradation of petroleum hydrocarbons in aerated soils. Findings indicate that forced aeration, coupled with additions of nutrients and moisture, stimulate hydrocarbon-degrading microorganisms and present a feasible approach to bioremediation management.     

Rearrangements of 3-heterobicyclo[3.2.0]hept-6-enes

Studies directed at a synthesis of dihydrothiepin 1b have resulted in the elucidation of several factors which effect cyclobutene ring opening in the 3-heterobicyclo[3.2.0]hept-6-ene ring system. We report the unexpected rearrangement of 4a, 4b, 13b and 13c to the synthetically useful a-vinyl-2,5-dihydrothiophenes 7a, 7b, 15a and 15b, respectively. Conversion of 4a to 6 is suggested to occur by a 1,3-rearrangement of 4a to isomeric 3-thiabicyclo[3.2.0]hept-6-ene 19 followed by cyclobutene ring opening in 19.     

On tall cardinals and some related generalizations

We continue the study of tall cardinals and related notions begun by Hamkins in 2009 and answer three of his questions posed in that paper.     

The projected newton method for solving inverse eigenvalue problems - the case of multiple eigenvaues

This paper deals with the optimal solution of ill-posed linear problems, i.e..linear problems for which the solution operator is unbounded. We consider worst-case ar,and averagecase settings. Our main result is that algorithms having finite error (for a given setting) exist if and only if the solution operator is bounded (in that setting). In the worst-case setting, this means that there is no algorithm for solving ill-posed problems having finite error. In the average-case setting, this means that algorithms having finite error exist if and only lf the solution operator is bounded on the average. If the solution operator is bounded on the average, we find average-case optimal information of cardinality n and optimal algorithms using this information, and show that the average error of these algorithms tends to zero as n→∞. These results are then used to determine the [euro]-complexity, i.e., the minimal costof finding an [euro]-accurate approximation. In the worst-case setting, the [euro]comp1exity of an illposed problem is infinite for all [euro]>0; that is, we cannot find an approximation having finite error and finite cost. In the average-case setting, the [euro]-complexity of an ill-posed problem is infinite for all [euro]>0 iff the solution operator is not bounded on the average, moreover, if the the solutionoperator is bounded on the average, then the [euro]-complexity is finite for all [euro]>0.