Does ionized diacetylene have a positive proton affinity?

Singly and doubly charged C₄H₃^+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C₄H₃²⁺ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IE_v(C₄H₃⁺)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IE_a(C₄H₃⁺)=16.33 eV and IE_v(C₄H₃⁺)=16.49 eV for the most stable isomer H₂C=C---CCH⁺. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C₄H₂⁺ has indeed a positive proton affinity of PA(C₄H₂⁺)=1.50±0.42 eV.     

Stereochemical features of the physical and chemical interactions of singlet oxygen with enecarbamates

Oxazolidinone-substituted enecarbamates represent a mechanistically rich system for the study of stereoelectronic, steric, and conformational effects on stereoselectivity and mode selectivity in (1)O(2) [2 + 2] and ene reactions. Photooxygenation of these enecarbamates with (1)O(2) leads to diastereomerically pure dioxetanes that decompose to yield an oxazolidinone carbaldehyde and one of the two enantiomers of methyldesoxybenzoin in enantiomeric excess. Stereoselectivity originates at the allylic stereocenter, a result supported by quenching studies, computational analysis, and deuterium solvent isotope effects. [reaction: see text]     

Liquid chromatography tandem mass spectrometry determination of free and conjugated estrogens in breast cancer patients before and after exemestane treatment

We report liquid chromatographic separation with tandem mass spectrometry determination of 12 endogenous estrogens and their intact conjugates in blood and urine and its application to study effects of exemestane treatment on estrogen generation and metabolism in postmenopausal women with estrogen-dependent breast cancer. A 0.5 mL aliquot of each urine or serum sample is fractionated with solid phase extraction to a fraction of free estrogen and another fraction of their conjugates. The reversed phase LC/MS/MS determines dansylated estrogens with positive ionization and intact conjugates with negative ionization. The method provides reproducible separation and limit of detection as low as 1 pg mL⁻¹ for free estrogens and 0.03 ng mg⁻¹ creatinine for the conjugates in serum and urine samples. The method enabled us to acquire unique concentration profiles of 12 endogenous estrogens and their intact conjugates in 30 breast cancer patients before and after one month of exemestane treatment. Exemestane suppressed total serum and urinary estrogens by 11–97% (P < 0.0001) and 8.7–91% (P < 0.0001), respectively. Specifically, these data show that exemestane preferentially suppressed E1, E1-3S, E1-3G, and E2-17G more than other estrogens. Linear regression analysis of estrogen concentrations before and after treatment showed correlation coefficients of 0.8385 (n = 289, P < 0.0001) and 0.8863 (n = 360, P < 0.0001). This study provides urinary and blood estrogen concentration profiles in breast cancer patients to demonstrate the effect of exemestane on estrogen generation, supporting inhibition of aromatase activity.     

Selective Formation of Metastable Ferrihydrite in the Chiton Tooth

Metastable precursors are thought to play a major role in the ability of organisms to create mineralized tissues. Of particular interest are the hard and abrasion‐resistant teeth formed by chitons, a class of rock‐grazing mollusks. The formation of chiton teeth relies on the precipitation of metastable ferrihydrite (Fh) in an organic scaffold as a precursor to magnetite. In vitro synthesis of Fh under physiological conditions has been challenging. Using a combination of X‐ray absorption and electron paramagnetic resonance spectroscopy, we show that, prior to Fh formation in the chiton tooth, iron ions are complexed by the organic matrix. In vitro experiments demonstrate that such complexes facilitate the formation of Fh under physiological conditions. These results indicate that acidic molecules may be integral to controlling Fh formation in the chiton tooth. This biological approach to polymorph selection is not limited to specialized proteins and can be expropriated using simple chemistry.     

The Potent Oxidant Anticancer Activity of Organoiridium Catalysts

Platinum complexes are the most widely used anticancer drugs; however, new generations of agents are needed. The organoiridium(III) complex [(η⁵‐Cp^xbiph)Ir(phpy)(Cl)] ( 1‐Cl ), which contains π‐bonded biphenyltetramethylcyclopentadienyl (Cp^xbiph) and C^N‐chelated phenylpyridine (phpy) ligands, undergoes rapid hydrolysis of the chlorido ligand. In contrast, the pyridine complex [(η⁵‐Cp^xbiph)Ir(phpy)(py)]⁺ ( 1‐py ) aquates slowly, and is more potent (in nanomolar amounts) than both 1‐Cl and cisplatin towards a wide range of cancer cells. The pyridine ligand protects 1‐py from rapid reaction with intracellular glutathione. The high potency of 1‐py correlates with its ability to increase substantially the level of reactive oxygen species (ROS) in cancer cells. The unprecedented ability of these iridium complexes to generate H₂O₂ by catalytic hydride transfer from the coenzyme NADH to oxygen is demonstrated. Such organoiridium complexes are promising as a new generation of anticancer drugs for effective oxidant therapy.     

[12] ane N_3-based BODIPY as a selective and sensitive off–on sensor for the sequential recognition of Cu~(2+) ions and ADP

A novel [12]aneN3-based BODIPY sensor 1 can be applied in the sequential recognition of Cu2 and ADP in aqueous solution and living cells with high selectivity and sensitivity     

Small molecular logic systems can draw the outlines of objects via edge visualization

The recently-discovered ability of small logical molecules to recognize edges is exploited to achieve outline drawing from binary templates. Outlines of arbitrary curvature, several colours and thicknesses down to 1 mm are drawn in around 30 min or less by employing a common laboratory two-colour ultraviolet lamp. The outlines and the light dose-driven XOR logic with fluorescence output or ‘off–on–off’ action which is observed in the irradiated regions are modelled by combining foundational principles of photochemistry, acid–base neutralization and diffusion.     

Free radical polymerization of caffeine‐containing methacrylate monomers

The incorporation of acrylic functionality into caffeine enables the preparation of a vast array of novel thermoplastics and thermosets. A two‐step derivatization provided a novel caffeine‐containing methacrylate monomer capable of free radical polymerization. Copolymers of 2‐ethylhexyl methacrylate and caffeine methacrylate (CMA) allowed for a systematic study of the effect of covalently bound caffeine on polymer properties. ¹H NMR and UV‐vis spectroscopy confirmed caffeine incorporation at 5 and 13 mol %, and SEC revealed the formation of high molecular weight (co)polymers (>40,000 g/mol). CMA incorporation resulted in a multistep degradation profile with initial mass loss closely correlating to caffeine content. Differential scanning calorimetry, rheological, and thermomechanical analysis demonstrated that relatively low levels of CMA increased the glass transition temperature, resulting in higher moduli and elucidating the benefits of incorporating caffeine into polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2829–2837     

Ultrasound‐assisted emulsification microextraction coupled with high‐performance liquid chromatography for the simultaneous determination of fragrance allergens in cosmetics and water

A simple, inexpensive, and environmentally friendly method based on ultrasound‐assisted emulsification microextraction followed by solidification of floating organic drop and high‐performance liquid chromatography coupled to diode array detection was developed for the simultaneous determination of 18 potentially allergenic fragrance substances. Several parameters affecting the microextraction process were investigated in detail by the “one‐variable‐at‐a‐time” approach. Optimal conditions were the following: 50 μL of 2‐dodecanol as extraction solvent, 10 mL of sample containing 150 g/L of salt, and 5 min of sonication at 35°C. Under the optimized conditions, method showed good linearity in the selected ranges, with squared correlation coefficients ranging from 0.948 to 0.999. Limits of detection ranged from 0.001 to 0.154 μg/mL and enrichment factors from 9 to 237. Precision of the method, expressed as relative standard deviation, was checked at two levels obtaining good results (3.3–14.4%). Recovery studies were made in baby bath water and in eau de cologne showing acceptable accuracy. Finally, the developed method was successfully applied to different commercial cosmetic and water samples. The most commonly found analyte was linalool followed by cinnamal and lilial. Most of the analyzed samples contained at least one of the target compounds.