Catalytic C−H Trifluoromethoxylation of Arenes and Heteroarenes

The intermolecular C?H trifluoromethoxylation of arenes remains a long‐standing and unsolved problem in organic synthesis. Herein, we report the first catalytic protocol employing a novel trifluoromethoxylating reagent and redox‐active catalysts for the direct (hetero)aryl C?H trifluoromethoxylation. Our approach is operationally simple, proceeds at room temperature, uses easy‐to‐handle reagents, requires only 0.03 mol % of redox‐active catalysts, does not need specialized reaction apparatus, and tolerates a wide variety of functional groups and complex structures such as sugars and natural product derivatives. Importantly, both ground‐state and photoexcited redox‐active catalysts are effective. Detailed computational and experimental studies suggest a unique reaction pathway where photoexcitation of the trifluoromethoxylating reagent releases the OCF₃ radical that is trapped by (hetero)arenes. The resulting cyclohexadienyl radicals are oxidized by redox‐active catalysts and deprotonated to form the desired products of trifluoromethoxylation.     

Determination of dissolved thiols using solid-phase extraction and liquid chromatographic determination of fluorescently derivatized thiolic compounds

A method employing solid-phase extraction coupled with HPLC separation of thiol-monobromobimane (mBBr) derivatives was developed and optimized to quantify dissolved thiols at concentrations as low as 0.1 nM for glutathione (GSH) and gamma-glutamylcysteine (gammaEC) in natural waters. The reducing reagent, tri-n-butylphosphine (TBP), is needed for complete derivatization. At the optimal addition of TBP ([TBP]/[mBBr] = -0.4-1.6), no interference from copper was observed. The thiol fluorescence signal was totally suppressed if the mole ratio of TBP to mBBr was 2.6 or greater. Consistent recovery of thiols standards in a NaCl solution (0.5 M) was obtained using the Waters HLB reversed-phase resin, and blank levels of GSH and gammaEC were extremely low (less than 0.03 nM). The detection limits for GSH, gammaEC and phytochelatin-2 (PC-2) were 0.03, 0.03, and 0.06 nM, respectively.     

Determination of Internal Energy Distributions of Laser Electrospray Mass Spectrometry using Thermometer Ions and Other Biomolecules

The internal energy distributions for dried and liquid samples that were vaporized with femtosecond duration laser pulses centered at 800 nm and postionized by electrospray ionization-mass spectrometry (LEMS) were measured and compared with conventional electrospray ionization mass spectrometry (ESI-MS). The internal energies of the mass spectral techniques were determined by plotting the ratio of the intact parent molecular features to all integrated ion intensities of the fragments as a function of collisional energy using benzylpyridinium salts and peptides. Measurements of dried p-substituted benzylpyridinium salts using LEMS resulted in a greater extent of fragmentation in addition to the benzyl cation. The mean relative internal energies, int> were determined to be 1.62?±?0.06, 2.0?±?0.5, and 1.6?±?0.3 eV for ESI-MS, dried LEMS, and liquid LEMS studies, respectively. Two-photon resonances with the laser pulses likely caused lower survival yields in LEMS analyses of dried samples but not liquid samples. In studies with larger biomolecules, LEMS analyses of dried samples from glass showed a decrease in survival yield compared with conventional ESI-MS for leucine enkephalin and bradykinin of ~15% and 11%, respectively. The survival yields for liquid LEMS analyses were comparable to or better than ESI-MS for benzylpyridinium salts and large biomolecules. Figure

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Asphaltene precipitation from latin american heavy crude oils. Effects of solvent aromaticity and agitation on particle size reduction

Asphaltenes from three crudes were precipitated with a mixture of n-heptane and toluene, the size of the particles formed under different solvent mixtures and different agitation regimes were studied. The kinetic size reduction of aggregates formed with an excess of precipitant agent is followed, contrary to other published studies where the kinetic followed is of growing particles. It was found that the particle size of precipitated asphaltenes decreases as precipitant aromaticity increases and agitation energy rises, which indicates the formation of aggregates bonded by weak forces, since the agitation applied was not of high energy, except for the ultrasonic device.     

Cytotoxic Coumarins from the Bark of Mammea siamensis

A new geranylated coumarin, (E)-4-(1-hydroxypropyl)-5,7-dihydroxy-6-(3,7-dimethyl-2,6-octadienyl)-8-(3-methyl-1-oxobutyl)coumarin (named surangin D), was isolated from the bark of Mammea siamensis collected in Vietnam, along with four known coumarins, surangins B and C, and theraphins B and C, and seven xanthones, 1,7-dihydroxyxanthone, 7-hydroxy-1-methoxyxanthone, 1,7-dimethoxyxanthone, 1,7-dimethoxy-6-hydroxyxanthone, 1,6,7-trihydroxyxanthone, 1,3,7-trihydroxyxanthone, and 1,7-dihydroxy-3-methoxyxanthone. Their structures were determined by spectroscopic methods (mainly 1D- and 2D-NMR) and preparation of methylated derivatives. The four coumarins, surangins C and D and theraphins B and C, were tested for inhibition of cell proliferation in DLD-1 (colon cancer), MCF-7 (breast adenocarcinoma), HeLa (human cervical cancer) and NCI-H460 (human lung cancer) cell lines using the sulforhodamine B (SRB) assay. In all four cell lines, theraphin C showed the strongest activity (IC?? in the range of 1.6-5.7 μM). Testing the anti-proliferative effect of the methylated derivatives showed reduced cellular effects of all derivatives, indicating that the number and position of free hydroxyl groups were very important for the anti-proliferative effect.     

Existence and multiplicity for positive solutions of a second-order multi-point discrete boundary value problem

We investigate the existence and multiplicity of positive solutions for a system of nonlinear second-order difference equations with multi-point boundary conditions.     

Positive solutions for a system of second-order multi-point boundary value problems

In this paper, we present some results for positive solutions of a system of nonlinear second-order ordinary differential equations subject to multi-point boundary conditions.     

Dynamic boundary value problems of the second-order: Bernstein–Nagumo conditions and solvability

This article analyzes the solvability of second-order, nonlinear dynamic boundary value problems (BVPs) on time scales. New Bernstein–Nagumo conditions are developed that guarantee an a priori bound on the delta derivative of potential solutions to the BVPs under consideration. Topological methods are then employed to gain solvability.     

Synthesis and identification of new thieno[3,2-b] benzothiophenes

The reaction of 2-lithiobenzo[b]thiophenes with ketones produced 2-hydroxyalkylbenzo[b]thiophenes which were cyclized in thionyl chloride to give novel thieno[3,2-b][1]benzothiophenes. Oxidation with peroxyacetic acid gave the S,S-dioxides whose regiochemistry was identified from ¹H nmr model studies using substituted benzo[b]thiophenes and their corresponding-1,1-dioxides [1].