Decarbopalladation of pi-allylpalladium intermediates formed from palladium-catalyzed arylations of 3-allen-1-ols

[reaction: see text] Unusual palladium-catalyzed arylative fragmentations of acyclic 3-allen-1-ols were observed. Oxidative addition of Pd(0) to aryl halides would form the arylpalladium halides, which added to the central carbon of allenes via carbopalladation to form the pi-allylpalladium intermediates. The pi-allylpalladium intermediates would be reductively eliminated via carbon-carbon cleavage to give the arylated dienes and the alpha-hydroxyalkylpalladium intermediates, which were further reductively eliminated to the corresponding aldehydes.     

Determination of buprenorphine by high-performance liquid chromatography with fluorescence detection: application to human and rabbit pharmacokinetic studies.

A rapid, sensitive, precise and accurate high-performance liquid chromatographic assay with fluorescence detection was developed for the determination of buprenorphine in human, rabbit, pig and dog plasma. It is comprised of only a one-step extraction procedure with hexane-isoamyl alcohol at pH 9.25 and reversed-phase chromatography on a muPorasil column. The recoveries of buprenorphine and nalbuphine (internal standard) were greater than 90%. Calibration graphs were linear over the concentration range 3-300 ng/ml with a coefficient of variation, both within-day and between-day, of less than 9% at any level. The limit of detection was 1.0 ng/ml of plasma based on a signal-to-noise ratio of 3. Eight other clinically used narcotics were investigated to check for potential interferences and their analytical conditions. The possible decomposed compounds of buprenorphine were also checked for the specificity of this assay. The method has been successfully applied to the stability and pharmacokinetic studies of buprenorphine. Buprenorphine in plasma did not decompose significantly at -20 degrees C for four weeks. Pharmacokinetic application in six rabbits and a surgical patient revealed that buprenorphine followed a linear three-compartment model with two distribution phases. The two distribution and elimination half-lives and the clearance of buprenorphine were 1.32, 24.8 and 230 min and 224 ml/min in human plasma, and 0.94, 12.5 and 232 min and 30 ml/min in rabbit plasma.     

Preparation of a highly active nanocrystalline TiO2 photocatalyst from titanium oxo cluster precursor

Nanocrystalline TiO₂ (sample S1) was prepared from a titanium oxo cluster (Ti₇O₄(OEt)₂₀) precursor via a sol-gel route. This photocatalyst showed a higher photocatalytic activity than the TiO₂ (sample S2) obtained from titanium tetraisopropoxide. The samples were characterized by thermal analysis (TGA/DSC), X-ray diffraction, micro-Raman spectroscopy, transmission electron microscopy, N₂ adsorption (BET surface area), infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy. The characterization results show that both samples are anatase nanocrystals with particle sizes of about 12 nm, but the more photocatalytically active sample S1 has more surface hydroxyl groups and larger surface area and pore volume than sample S2.     

Pretreatment of swine wastewater using anaerobic filter

Efforts were made to assess the efficiency of an anaerobic filter packed with porous floating ceramic media and to identify the optimum operational condition of anaerobic filter as a pretreatment of swine wastewater for the subsequent biological removal of nitrogen and phosphorus. A stepwise decrease in hydraulic retention time (HRT) and an increase in organic loading rate (OLR) were utilized in an anaerobic filter reactor at mesophilic temperature (35°C). The optimum operating condition of the anaerobic filter was found to be at an HRT of 1 d. A soluble chemical oxygen demand (COD) removal efficiency of 62% and a total suspended solids removal efficiency of 39% at an HRT of 1 d were achieved with an OLR of 16.0 kg total COD/(m³·d), respectively. The maximum methane production rate approached 1.70 vol of biogas produced per volume of reactor per day at an HRT of 1 d. It was likely that the effluent COD/total Kjeldahl nitrogen ratio, of 22, the COD/total phosphorous ratio of 47, and the high effluent alkalinity >2500 mg/L as CaCO₃ of the anaerobic filter operated at an HRT of 1 d was adequate for the subsequent biological removal of nitrogen and phosphorus.     

Extraction of phenolic compounds and organic acids by liquid membranes

Liquid membrane emulsions were used to extract phenolic compounds and organic acids from their aqueous solutions. The emulsions contained caustic as the reactive agent. When the phenolic compounds and organic acids permeated through the liquid membranes into the emulsion droplets, they reacted with caustic and became ionized. The ionized species could not permeate through the liquid membranes and therefore were held in the emulsion droplets.

The conclusions of this recent investigation are:

(1) More than 99% of phenol and cresols can be extracted in less than 1 minute.

(2) Acetic and propionic acids can also be extracted but at much slower rates. However, if the amount of caustic is not sufficient to react with all the permeating compounds, the acids will be extracted preferentially to the phenols.

(3) The acids can only be extracted at low pH (acidic) whereas the phenolic compounds can be extracted at pH of 7.

(4) The extraction rates for phenol and acetic acid are the same in individual-compound and binary-mixture permeations.

(5) The extraction can be described by a mass transfer model.     

Vibronic states in single molecules: C60 and C70 on ultrathin Al2O3 films

Vibronic states are observed in single C(60) and C(70) molecules by scanning tunneling microscopy. When single fullerene molecules are adsorbed on a thin layer of Al(2)O(3) grown on a NiAl(110) substrate, equally spaced features are observed in the differential conductance (dI/dV), which are clearly resolved in d(2)I/dV(2) spectra. These features are attributed to the vibronic states of the molecule. The vibronic progressions are sensitive to the molecular orientations and can have different spacings in different electronic bands of the same molecule. For C(60,) these vibronic states are associated with the intramolecular A(g) and H(g) vibrational modes. Vibronic states are not resolved in molecules adsorbed on the metal surface. However, inelastic electron tunneling spectroscopy exhibits a vibrational mode at 64 meV for C(60) and 61 meV for C(70) adsorbed on NiAl(110).     

Simple mimetics of a nuclear localization signal (NLS)

[reaction: see text] Molecular modeling was used to design mimetics of the HIV-1 matrix protein nuclear localization signal (NLS) in which a scaffold of two resorcinol units joined by a diamide linker presents 3-aminopropyl ethers in place of lysine side chains. Prospective mimetics with linkers of 6, 8, 10, or 12 atoms were synthesized and compared in a competition assay for binding to the nuclear import receptor subunit karyopherin alpha, showing the 10-atom linker to be best and shorter ones ineffective.     

The inverted cucurbit[n]uril family

We report the isolation, characterization, and recognition behavior of iCB[6] and iCB[7], which are diastereomers of CB[6] and CB[7], respectively, containing a single inverted glycoluril unit. Product resubmission experiments establish that these inverted CB[n] are intermediates in the mechanism of CB[n] formation. As a consequence of the inverted glycoluril ring, these inverted cucurbiturils possess a permanent dipole moment, are slightly smaller than their diastereomers, show distinctive selectivity in their recognition behavior, and report directly on the contents of their hydrophobic cavity.     

Synthesis and Cytotoxicity Evaluation of Metal‐Chelator‐Bearing Flavone,Carbazole, Dibenzofuran,Xanthone, and Anthraquinone

2‐(Aryloxymethyl)‐5‐benzyloxy‐1‐methyl‐1H‐pyridin‐4‐ones 8a – 8g , 2‐(aryloxymethyl)‐5‐hydroxy‐4H‐pyran‐4‐ones 9a – 9g , and 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were prepared from the known 5‐benzyloxy‐2‐(hydroxymethyl)pyran‐4‐one ( 3 ) in a good overall yield. These compounds were evaluated in vitro against a three‐cell lines panel consisting of MCF7 (breast), NCI‐H460 (lung), and SF‐268 (CNS), and the active compounds passed on for evaluation in the full panel of 60 human tumor cell lines derived from nine cancer cell types. The results indicated that 5‐hydroxy derivatives are more favorable than their corresponding 5‐benzyloxy precursors ( 10a – 10g vs. 8a – 8g ), and 1‐methyl‐1H‐pyridin‐4‐ones are more favorable than their corresponding pyran‐4(1H)‐ones ( 10a – 10g vs. 9a – 9g ). Among these three types of compounds, 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were the most cytotoxic; they inhibited the growth of almost all the cancer cells tested. On the contrary, compound 8a (a mean GI₅₀=27.8 μM ), 8b (38.5), 8d (11.0), and 8e (30.5) are especially active against the growth of SK‐MEL‐5 (a melanoma cancer cell) with a GI₅₀ of <0.01, 5.65, 0.55, and 0.03 μM , respectively (cf. Table 2).     

Seasonal variation and activity size distribution of <Superscript>7</Superscript>Be in ambient air

The seasonal variation of the ⁷Be activities in air and the size distribution of the ⁷Be aerosols were studied by using a continuous air sampler and a five stage cascade impactor. The mean monthly activity level of ⁷Be at the Korea Atomic Energy Research Institute (KAERI) site varied from 0.5 to 4.8 Bq·m⁻³ and revealed a seasonal variation, in which the ⁷Be activity levels were high in winter and low in summer. The mass size distribution showed a bi-modal distribution with a higher peak around 0.49 μm and a smaller peak between 3 μm and 7.2 μm. The activity median aerodynamic diameter (AMAD) decreased with increasing ambient ⁷Be concentrations. The mean residence times by using a mean growth rate of 0.004 μm·h⁻¹ were estimated to be 2.5–6.4 days. The AMAD has an increasing tendency with higher relative humidity. It seemed that the high humidity condition facilitated the growth of the aerosol, resulting in increased deposition rates of the aerosols and the low ⁷Be content in the surface air. The AMAD of the ⁷Be aerosols increased with an increasing temperature, but the temperature dependency of AMAD should be explained with geological and meteorological conditions.