Catalytic, highly enantio- and diastereoselective pinacol coupling reaction with a new tethered bis(8-quinolinolato) ligand

A new class of chiral ligand, tethered bis(8-quinolinol) (TBOxH), is developed. Its chromium complex, TBOxCrCl (3 mol %), effectively catalyzes the pinacol coupling reaction of aromatic aldehydes at room temperature with high yield (up to 94%), high diastereoselectivity (up to dl:meso = 98:2), and high enantioselectivity (up to 98%). The scope of the present method turns out not to be limited to aromatic aldehyde derivatives, as cyclohexanecarboxaldehyde undergoes pinacolization as well (44% yield, dl:meso = 93:7, 84% ee). The method provides an efficient access to enantioenriched 1,2-diols.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Reaction of tetraazathiapentalene and thiadiazolopyrimidine derivatives with heterocumulenes: Cycloaddition and elimination reactions via hypervalent sulfur intermediates

Tetraazathiapentalene derivative 1 reacts with heterocumulenes such as diphenylketene (2) and 2‐pyridylisothiocyanate (5) to give heterocycles 3, 6 and 7 with elimination of methylisothiocyanate. The reactions of thiadiazolopyrimidine derivatives 8a‐b with ethoxycarbonyl isothiocyanate (9) and carbon disulfide (11) gives heterocycles 10 and 12 via thermal decomposition of 1:1 cycloadducts C and D which have a hypervalent sulfur. The mechanistic and reactivity features of these reactions are described.     

Determination of Low-Level Ethylenediaminetetraacetic Acid in Water Samples by Ion Chromatography with Ultraviolet Detection

A convenient and sensitive ion chromatographic (IC) method for the analysis of ethylenediaminetetraacetic acid (EDTA) in water samples was proposed. Using a fast reversible reaction of free EDTA and metal–EDTA complexes into Fe(III)–EDTA complex in the presence of Fe(III) ions, sample solutions were applied to an ion-exchange column using a mobile phase (pH 2.3), which was composed of 100 μM Fe(III) chloride and 5 mM methanesulfonic acid. The addition of Fe(III) solution (100 μL) containing 10 mM Fe(III) chloride and 0.5 M methanesulfonic acid to the sample solution (10 mL) permitted the injection of a large volume (400 μL) of sample, which allowed for greater sensitivity. The proposed IC method gave a highly linear (r ² > 0.999) calibration curve ranging 0.005–1.0 μM EDTA and had a limit of detection of 1.5 nM. High repeatability (RSD < 2.1%) and recoveries (88–108%) were also obtained. With this method, total EDTA level in raw and drinking waters were analyzed successfully.     

Photoinduced ionic polymerization. VII. Cationic polymerization of cyclohexene oxide in solid state

Photopolymerization of cyclohexene oxide in the presence of electron acceptors was studied in a bulk system (in liquid as well as in solid states). The polymerization was proved to proceed by a cationic mechanism in both states by the effect of inhibitors. In a liquid phase the light intensity dependence of the rate of polymerization and the molecular weight distribution showed a contribution of a free ionic polymerization. Any discontinuous phenomenon in the rate as well as in the molecular weight was not discerned between liquid(above ?36°C) and plastic crystal (between ?36 and ?81°C) phases. A quantum yield of monomer consumption as high as 8 × 10³ was observed in the plastic crystal phase. Below ?81°C in the normal crystal phase the rate as well as the molecular weight was remarkably suppressed.     

Fibrinolytic effect of tissue plasminogen activator on cerebral embolism in stroke-prone spontaneously hypertensive rats.

To study the thrombolytic effect of tissue plasminogen activator (t-PA) on cerebral emboli, we characterized cerebral embolization in stroke-prone spontaneously hypertensive rats (SHRSPs) and Wistar Kyoto rats (WKYs). [125I]Fibrin clot particles (20-100 microns diameter) were injected twice at an interval of 90 min into the left internal carotid artery of WKYs and SHRSPs. After each injection, spontaneous embolus dissolution was monitored with a gamma-ray detector placed on the head of the embolic rats. Embolus dissolution was spontaneously generated in 15 min after the injection of fibrin clots. In WKYs, 21% and 42% of the clots were dissolved 30 and 90 min after the second embolization, respectively. On the other hand, the spontaneous embolus dissolution in SHRSPs was significantly lower than that of WKYs, indicating that the endogenous fibrinolytic ability of SHRSPs is less potent than that of normotensive rats. The intravenous administration of t-PA at doses of 75, 250 and 750 micrograms/kg caused a dose-dependent embolus dissolution in SHRSPs. Furthermore, systematically applied t-PA produced embolus dissolution without causing systemic plasminogen activation, fibrinogen breakdown or bleeding. In conclusion, the intravenous administration of t-PA produces selective embolus dissolution without systemic fibrino(geno)lysis in a cerebral embolic SHRSP.     

Selective reduction of tertiary alkyl,benzyl, and allyl halides to hydrocarbons using lithium 9,9-di-n-butyl-9-borabicyclo[3.3.1]nonanate

The title 9-borabicyclo[3.3.1]nonane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives. The reduction of cis- and trans - 4 - t - butyl - 1 - methylcyclohexyl chlorides (2) with 1 gives 4 - t - butyl - 1 - methylcyclohexanes (3) with partial inversion of configuration in cyclohexane, while that in benzene gives thermodynamically stable trans-3 predominantly. The reactions of 1,1 - dimethyl - 5 - hexenyl chloride (4) and 1,7,7 - trimethylbicyclo[2.2.1]hept - 2 - yl chloride (8) with 1 proceed with the rearrangements characteristic to a carbonium ion intermediate. The reduction of 1 - ethyl - 1 - methylpentyl chloride with 1 follows a second-order rate equation.     

Determination of sulfates of androsterone and epiandrosterone in human serum using isotope diluted liquid chromatography-electrospray ionization-mass spectrometry

A promising liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for analysis of the sulfates of 5alpha-androgen, androsterone and epiandrosterone (A-S and EpiA-S) in human serum was developed. The method was used to assess one of the markers of 5alpha-reductase activity of males including patients with prostate cancer (PC). After deproteinization with acetonitrile, the androgen sulfates and the internal standard, [7,7,16,16-2H4]dehydroepiandrosterone-S, were extracted from human serum using a solid-phase extraction cartridge and washed with hexane. The extract was reconstituted and applied to the LC/ESI-MS system operated in the selected ion monitoring mode. The method was validated over the range 0.02-5 microg/mL (A-S) and 0.005-1.5 microg/mL (EpiA-S) using 10 microL of human serum. The method was a concise procedure without chemical or enzymatic hydrolysis of the conjugates, purification by high-performance liquid chromatography and/or derivatization, and proved to be satisfactory in its reproducibility and accuracy. The levels of these androgen sulfates tended to decrease during aging, and the A-S levels in the sera obtained from both healthy males and patients with PC were correlated with their EpiA-S levels.     

Ligand-exchange ion chromatographic determination of malic acid enantiomers in apple juice with photometric detection.

An ion chromatographic separation with photometric detection using a chiral copper(II) complex as the eluent has been developed for the resolution of enantiomers of malic acid in commercially available apple juices. The results obtained by this method were in good agreement with those by an enzymatic method with separation by high-performance liquid chromatography.     

High pressure and high temperature investigations in the system MgOSiO2H2O

The system MgOSiO₂H₂O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H₆Mg₇Si₂O₁₄. When the $\text{Mg}\text{Si}$ ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the $\text{Mg}\text{Si}$ ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P6₃ or $\text{P6}{}_3\text{m}$ and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm³. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group $\text{P2}{}_1\text{c}$ with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.