Plasmonic monitoring of catalytic hydrogen generation by a single nanoparticle probe

Plasmonic nanostructures such as gold nanoparticles are very useful for monitoring chemical reactions because their optical properties are highly dependent upon the environment surrounding the particle surface. Here, we designed the catalytic structure composed of platinized cadmium sulfide with gold domains as a sensitive probe, and we monitored the photocatalytic decomposition of lactic acid to generate hydrogen gas in situ by single-particle dark-field spectroscopy. The plasmon band shift of the gold probe throughout the reaction exhibits significant particle-to-particle variation, and by simulating the reaction kinetics, the rate constant and structural information (including the diffusion coefficient through the shell and the relative arrangement of the active sites) can be estimated for individual catalyst particles. This approach is versatile for the monitoring of various heterogeneous reactions with distinct components at a single-particle level.     

A rapid and facile method for measuring corrosion rates using dynamic light scattering

A dynamic light scattering (DLS) method was adopted for measuring the corrosion of iron nanoparticles. The average diameter of the nanoparticles in a sodium chloride suspension increased linearly with time as iron oxide layers formed around the nanoparticles. The nanoparticle corrosion rate determined by DLS was found to be almost identical to the value obtained by conventional immersion tests (ASTM G31). The DLS method offers the advantage that measurements may be completed within several hours under natural corrosion conditions whereas the conventional immersion method requires several months. Application of the DLS method to alloy nanoparticles with a variety of chromium compositions showed that the nanoparticle sizes changed nonlinearly over time, and the curves were best fit by a first order exponential function. The first order time constants were found to be linearly related to the corrosion rates determined by ASTM G31.     

Quantitative and Qualitative Analysis of CKD-501, Lobeglitazone, in Human Plasma and Urine Using LC–MS/MS and Its Application to a Pharmacokinetic Study

A simple, rapid and sensitive LC–MS/MS method in positive ion mode was developed and validated to determine CKD-501, lobeglitazone, in human plasma and urine using glipizide as an internal standard (IS). Lobeglitazone is a novel thiazolidinedione (TZDs)-based peroxisome proliferator-activated receptor (PPAR) agonist, used for the management of type-2 diabetes. After mixing the IS, dissolved in acetonitrile, with a plasma or urine sample containing lobeglitazone, 10?μL of supernatant was injected into the LC–MS/MS system. Quantification was performed in the multiple reaction monitoring (MRM) mode using transition of 481.5?→?152.2 (m/z) for lobeglitazone and 446.1?→?321.2 (m/z) for the IS. The method showed good linearity over concentration ranges of 0.5–1,000?ng?mL^?1 for plasma and 0.2–250?ng?mL^?1 for urine (r ²?≥?0.9996). The mean percent extraction recovery of lobeglitazone was 90.8?% for plasma and 87.3?% for urine, while the recoveries of the IS were greater than 86.4?% for both. The intra-day and inter-day precision of plasma ranged from 1.1 to 3.7 and 2.5 to 3.3?% (RSD), respectively, and the intra- and inter-day precision of urine ranged from 1.5 to 2.7 and 3.2 to 3.5?%, respectively. This method is simple, sensitive, and applicable for the pharmacokinetic study of lobeglitazone in human plasma. Most of the urine concentrations of lobeglitazone were below the LLOQ because the lobeglitazone is extensively metabolized.     

Eight New 2‐(2‐Phenylethyl)chromone (=2‐(2‐Phenylethyl)‐4H‐1‐benzopyran‐4‐one) Derivatives from Aquilaria malaccensis Agarwood

Eight new and eight known 2‐(2‐phenylethyl)chromone (=2‐(2‐phenylethyl)‐4H‐1‐benzopyran‐4‐one) derivatives, i.e., 1 – 8 and 9 – 16 , respectively, together with the two known sesquiterpenoids 17 and 18 were isolated from a 70% MeOH extract of Aquilaria malaccensis (AM) agarwood chips. Their structures were determined based on extensive spectroscopic analysis and comparison with reported data.     

Chemical Composition, Antioxidant and Anticancer Effects of the Seeds and Leaves of Indigo (Polygonum tinctorium Ait.) Plant

Seeds and leaves of indigo (Polygonum tinctorium Ait.) plant were investigated and compared with another medicinal plant named prolipid for their properties such as chemical composition, antioxidant, and anticancer effects by Fourier transform infrared, three-dimensional fluorescence spectroscopy, and electrospray ionization-MS in negative mode. It was found that polyphenols, flavonoids, and flavanols were significantly higher in prolipid (P?<?0.05), following by indigo mature leaves, immature leaves, and seeds. Methanol extract of mature indigo leaves in comparison with the ethyl acetate extract showed higher inhibition of proliferation. The interaction between polyphenol extracts of indigo mature leaves and BSA showed that indigo has a strong ability, as other widely used medicinal plants, to quench the intrinsic fluorescence of BSA by forming complexes. In conclusion, indigo mature leaves were compared with prolipid. High content of bioactive compounds, antioxidant, fluorescence, and antiproliferative properties of indigo justifies the use of this plant as a medicinal plant and a new source of antioxidants.     

Solvation of LiClO4 and NaClO4 in deuterated acetonitrile studied by means of infrared and Raman spectroscopy

Vibrational characteristics of CD3CN solutions of LiClO4 and NaClO4 have been studied by means of infrared and Raman spectroscopy. Blue shifts of 22 and 11 cm(-1) of the v2 C[triple bond]N stretch are observed resulting from interaction of CD3CN with Li+ and Na+, respectively. The number of primary solvation sites of both Li+ and Na+ in acetonitrile is believed to be four from the comparison of the Raman intensities of the C[triple bond]N stretch for free CD3CN and those coordinated to Li+ and Na+. Evidently formation of contact ion pairs of the cation (Li+ or Na+) and anion (ClO4-) is more probable at a higher concentration of the salt. The characteristics of the v2 C[triple bond]N stretch, v4 C-C stretch, and v8 CCN deformation bands vary substantially upon coordination, while other vibrational bands are relatively immune to the donor-acceptor interaction. DFT calculations have also been performed at the BLYP/6-31 + G(2d,p) level to examine the structures and vibrational characteristics of CD3CN coordinated to Li+ and Na+. The calculated results are in good agreement with the observed vibrational characteristics.     

Abnormal spin-pumping effect at Pt/NiFe interface by an oxidation of ferromagnet

The Inverse Spin Hall Effect (ISHE) voltage induced by spin-pumping was measured in Pt/[nonoxidized or oxidized NiFe] samples. The spectrum shape of the DC voltage signal was well-reproduced by simple Lorentzian functions, which were consistent with the prediction of ISHE in Pt/nonoxidized NiFe sample. On the other hand, the voltage signal from the Pt/oxidized NiFe was significantly decreased in accordance with abnormal ferromagnetic resonance (FMR) behavior. The origin of the ISHE voltage degradation was investigated by the FMR spectrum and X-ray photoelectron spectroscopy (XPS) analyses. The spin-pumping was suppressed by the oxidation of NiFe layer and deficient Pt/NiFe interface. The well-defined ferromagnet and clear interface with a normal spin mixing conductance were experimentally demonstrated to be reasonable spin-pumping.     

Electrical behavior of amorphous indium–gallium–zinc oxide thin film transistors by embedding Au nanoparticles in the channel layer

We reported the effects on the electrical behavior of amorphous indium–gallium–zinc oxide (a-IGZO) thin film transistors (TFTs) after introducing various positions and sizes of Au nanoparticles (NPs) in the channel layer. These TFTs showed an off-current increase and threshold voltage (V_th) shift compared to conventional a-IGZO TFTs. The effects of Au NPs are explained to form the carrier conduction path which causes the current leakage in the channel layer, and act as either electron injection sites or trap sites. Therefore, this study demonstrates that the optimized control of size and position of Au NPs in the channel layer is crucial for its application in the electrical stability improvement and V_th control of a-IGZO TFTs.     

On the number of even and odd strings along the overpartitions of n

Recently, Andrews, Chan, Kim, and Osburn introduced the even strings and the odd strings in the overpartitions. We show that their conjecture $$A_k (n) \geq B_k (n)$$ holds for large enough positive integers n, where A _k (n) (resp. B _k (n)) is the number of odd (resp. even) strings along the overpartitions of n. We introduce m-strings and show how this new combinatorial object is related with another positivity conjecture of Andrews, Chan, Kim, and Osburn. Finally, we confirm that the positivity conjecture is also true for large enough integers.     

Green polymer chemistry using nature's catalysts,enzymes

The use of enzymes as catalysts for organic synthesis has become an increasingly attractive alternative to conventional chemical catalysis. Enzymes offer several advantages including high selectivity, ability to operate under mild conditions, catalyst recyclability, and biocompatibility. Although there are many examples in the literature involving enzymes for the synthesis of polymers, our search showed that very little had been done in the area of polymer modification. In this article, we will discuss enzyme catalysis in general and highlight our recent results concerning precision polymer functionalization using enzymatic catalysis—“green polymer chemistry.” © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2959–2976, 2009