Behaviors of chemical elements in the atmosphere,Kawasaki, Japan

A total of 19 elements in the samples of atmospheric deposition collected in Kawasaki, Japan, were determined by neutron activation analysis, ICPAES and flame photometry. The amounts of soil dust depositions were larger in springs and those of Sb and Zn depositions were larger in summers than in the other seasons. The values of the enrichment factors were higher for Sb and Zn than for the other elements determined throughout the sampling period. A factor analysis showed that the two elements were characterized as industrial components. Rubber products like tires that contain noncombustibles and rubber accelerators were a possible origin of high concentrations of Sb and Zn in the present samples.     

Remotely triggered liposome release by near-infrared light absorption via hollow gold nanoshells

An elusive goal for systemic drug delivery is to provide both spatial and temporal control of drug release. Liposomes have been evaluated as drug delivery vehicles for decades, but their clinical significance has been limited by slow release or poor availability of the encapsulated drug. Here we show that near-complete liposome release can be initiated within seconds by irradiating hollow gold nanoshells (HGNs) with a near-infrared (NIR) pulsed laser. Our findings reveal that different coupling methods such as having the HGNs tethered to, encapsulated within, or suspended freely outside the liposomes, all triggered liposome release but with different levels of efficiency. For the underlying content release mechanism, our experiments suggest that the microbubble formation and collapse due to the rapid temperature increase of the HGN is responsible for liposome disruption, as evidenced by the formation of solid gold particles after the NIR irradiation and the coincidence of a laser power threshold for both triggered release and pressure fluctuations in the solution associated with cavitation. These effects are similar to those induced by ultrasound and our approach is conceptually analogous to the use of optically triggered nano-"sonicators" deep inside the body for drug delivery. We expect HGNs can be coupled with any nanocarriers to promote spatially and temporally controlled drug release. In addition, the capability of external HGNs to permeabilize lipid membranes can facilitate the cellular uptake of macromolecules including proteins and DNA and allow for promising applications in gene therapy.     

Mechanism of metal chloride-promoted Mukaiyama aldol reactions

Ab initio calculations (MP2/6-311+G**//B3LYP/6-31G*) were employed to investigate the mechanism of metal chloride-promoted Mukaiyama aldol reaction between trihydrosilyl enol ether and formaldehyde. The metal chlorides considered include TiCl4, BCl3, AlCl3, and GaCl3. In contrast to the concerted pathway of the uncatalyzed aldol reaction, the Lewis acid-promoted reactions favor a stepwise mechanism. Three possible stepwise pathways were located. The lowest energy pathway corresponds to a simultaneous C-C bond formation and a chlorine atom shift in the first (rate-determining) step. This process is calculated to have a low activation barrier of 12 kJ mol-1 for the TiCl4-promoted reaction. The alternative [2+2] cycloaddition and direct carbon-carbon bond formation pathways are energetically competitive. BCl3, AlCl3, and GaCl3 are predicted to be efficient catalysts for the silicon-directed aldol reaction as they strongly activate the formaldehyde electrophile. Formation of a stable pretransition state intermolecular pi-pi complex between enol silane and the activated formaldehyde (CH2=O...MCln) is a key driving force for the facile metal chloride-promoted reactions.     

Ethenedithione (S=C=C=S): Does It Obey Hund's Rule?

Significantly higher in energy (24 kJ mol⁻¹) than the triplet ground state (³Σ_g⁻) is the ¹Δ_g state of ethenedithione (S=C=C=S), in agreement with Hund's rule. This result was obtained from high-level ab initio calculations. Thus, ethenedithione cannot, as had been proposed, be considered as the first example for the violation of Hund's rule in an equilibrium structure.     

Observation of 18O/16O isotope effects at the cathode of a polymer electrolyte membrane fuel cell

¹⁸O/¹⁶O isotope effects were observed at the cathode of a polymer electrolyte membrane fuel cell at 25 and 35°C. Results of experiments in which the ¹⁸O/¹⁶O isotope ratios of the oxygen gases supplied to and exhausted from the cell were measured revealed that the lighter isotope ¹⁶O reacted more preferentially to form water molecules at the cathode than the heavier one, ¹⁸O. The value of the oxygen isotope separation factor, S₁, defined as the ratio of the ¹⁸O/¹⁶O isotope ratios of the oxygen gases supplied to and exhausted from the cell, ranged from 1.0030 to 1.0139, and tended to decrease with decreasing rate of oxygen utilisation (θ) and with increasing flow rate of the feed oxygen gas (D_F). The value of another separation factor, S₂, defined as the ratio of the ¹⁸O/¹⁶O isotope ratios of the exhausted oxygen gas and oxygen having reacted to form water molecules at the cathode, ranged from 1.0049 to 1.0304. The S₂ value was much less affected by the change in θ and D_F than the S₁ value with the majority of the S₂ value being in the range of 1.0240–1.0304.     

Spot focus size effect in spectroscopic ellipsometry of thin films

A focused as opposed to collimated light beam is typically used as probe in order to achieve a smaller as well as more intense light interrogation area in spectroscopic ellipsometry of thin films. In this work, we performed geometric ray analysis at the illumination and recording ends of such a system. The numerical results revealed substantial changes in (i) average optical path length and (ii) optical path length differences, which varied according to wavelength despite the film thickness remaining uniform. These results were able to consistently explain the anomalies found when different focus probe beam sizes were used in experimental spectroscopic ellipsometry measurements.