Hydroxamic acids as weak base indicators: protonation in strong acid media.

The protonation equilibria of N-phenylbenzohydroxamic, benzohydroxamic, salicylhydroxamic, and N-p-tolylcinnamohydroxamic acids have been studied at 25 degrees C in concentrated sulfuric, hydrochloric, and perchloric acid media; the UV-vis spectral measurements were analyzed using the Hammett equation and the Bunnett-Olsen and excess acidity methods. The medium effects observed in the UV spectral curves were corrected with the Cox-Yates and vector analysis methods. The H(A) acidity function based on benzamides provided the best results. The range of variation of the solvation coefficient m is similar to that of amides, this indicating similar solvation requirements for amides and hydroxamic acids. For the same substrate, the observed variations of pK(BH)(+) with the mineral acid used was justified by formation of solvent-separated ion pairs; for the same mineral acid, the observed changes in pK(BH)(+) can be explained by the solvation of BH(+). The change of the pK(BH)(+) values was in reasonably good agreement with the sequence of the catalytic efficiency of the mineral acids used, HCl > H(2)SO(4) > HClO(4).     

Synthesis of 9-alkyl-6-amino[1,2,4]triazolo[3,4-c]-5-azaquinoxalines. Mild and effective SNAr amination of highly electron-poor heterocycles

The synthesis and characterization of five different 9-alkyl-6-amino[1,2,3]triazolo[3,4-c]-5-azaquinoxalines is described. Due to the notable electrophilic character of the C-6 position of the [1,2,4]triazolo[3,4-c]-5-azaquinoxaline tricyclic system, S_NAr amination was achieved simply by reacting the corresponding 6-chloro derivative with ammonia-saturated acetonitrile (a non-nucleophilic polar solvent) in a sealed reaction vessel, using microwave-mediated or conventional heating.     

Acrylic copolymers with pendant 1,2,4‐triazole moieties as colorimetric sensory materials and solid phases for the removal and sensing of cations from aqueous media

Linear water‐soluble polymers and nets with gel‐like behavior were prepared for use as colorimetric sensors and selective extracting agents for naked eye detection and solid–liquid removal of heavy‐metal cations from aqueous environments. Triazole is a well‐known, heavy‐metal cation host. A water‐insoluble methacrylamide containing a 1,2,4‐triazole receptor derivative was copolymerized with highly hydrophilic and water‐soluble methacrylamides to yield a water‐soluble polymer or a cross‐linked network as a powder or a dense membrane. In powder form, the material selectively removed Hg²⁺, Pb²⁺, and Ag⁺ from aqueous media. In the form of swelled dense membranes or films, the material acted as colorimetric sensor for Fe³⁺. When the membrane was soaked in a yellow aqueous solution of Fe³⁺, the former colorless, transparent membrane became reddish (but retained its transparency), and the solution became colorless. Aqueous conductivity studies confirmed that both the extraction and the sensing phenomena arose from the interaction of the cations with the triazole moieties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Ultrasonic‐assisted derivatization of estrogenic compounds in a cup horn booster and determination by GC‐MS

Cup horn boosters are miniaturized ultrasound baths that maximize efficiency and precision. The optimization of an ultrasonic‐assisted derivatization step by means of a cup horn booster and the determination of estrone, 17β‐estradiol, estriol, 17α‐ethynyl estradiol and mestranol was developed by GC‐MS. Different derivatization reagents and solvents were studied for maximizing the di‐derivatization of 17α‐ethynyl estradiol under ultrasound energy. Only N,O‐bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane in pyridine gave satisfactory results and this mixture was further used in the optimization of the ultrasound assisted derivatization. The experiment designs included sonication time (1–10 min), sonication power (20–80%), sonication cycles (1–9), derivatization reagent volume (25–125 μL) and solvent volume (25–125 μL). Once the optimum conditions were fixed, the effect of organic matter and the frequency of the water bath change were studied. Finally, the validation of the analytical method was carried out using spiked natural and synthetic waters. Recoveries (natural (138–70%) and synthetic (112–89%)), the LODs (0.35–1.66 ng/L), and LOQs (1.16–5.52 ng/L) and the precision (0.2–5.3%) of the method were studied. This is the first work in the literature where a cup horn booster is used with the aim of minimizing derivatization time during the determination of estrogenic compounds.     

State of the art in catalytic oxidation of chlorinated volatile organic compounds

Chlorine-containing organic compounds (Cl-VOC) require special attention due to their distinct toxicity, high stability and persistence in the environment. Removal of Cl-VOC by catalytic oxidation over a wide variety of catalysts has been presented in literature. This paper reviews the state of the art in this subject, including different model compounds, nature of catalysts, and oxidation activity. Catalyst selectivity (CO₂ vs. CO and HCl vs. Cl₂), by-products formation and the causes of deactivation are also analyzed as the most important factors in the catalyst selection for practical applications.     

Quasiparticle interference around a magnetic impurity on a surface with strong spin-orbit coupling

On surfaces with strong spin-orbit coupling, backscattering is forbidden since it requires flipping of the spin of the electron. It has been proposed that the forbidden scattering channels in such systems can be activated if time reversal symmetry is locally broken, for example, by a magnetic scattering center. Scanning tunneling spectroscopic maps of quasiparticle interference patterns around a single magnetic MnPc molecule on a Bi(110) surface reveal only spin-conserving scattering events. Simulations based on the Green's functions approach confirm that the charge-density interference patterns are unaffected by the magnetic state of the impurity. A fingerprint of backscattering processes appears, however, in the magnetization patterns, suggesting that only spin-polarized measurements can access this information.     

Inventory control of supply chains: Mitigating the bullwhip effect by centralized and decentralized Internal Model Control approaches

In this paper, a two-degrees-of-freedom Internal Model Control structure is incorporated in production inventory control for a supply chain system. This scheme presents an intuitive and simple parametrization of controllers, where inventory target tracking and disturbance (demand) rejection in the inventory level problems are treated separately. Moreover, considering that the lead times are known, this scheme presents a perfect compensation of the delay making the stabilization problem easier to handle. This control structure is formulated for a serial supply chain in two ways (by using a centralized and a decentralized control approach). The behavior of these inventory control strategies is analyzed in the entire supply chain. Analytical tuning rules for bullwhip effect avoidance are developed for both strategies. The results of controller evaluations demonstrate that centralized control approach enhances the behavior with respect to the inventory target tracking, demand rejection and bullwhip effect in the supply chain systems.     

Truly-Biocompatible Gold Catalysis Enables Vivo-Orthogonal Intra-CNS Release of Anxiolytics

Being recognized as the best-tolerated of all metals, the catalytic potential of gold (Au) has thus far been hindered by the ubiquitous presence of thiols in organisms. Herein we report the development of a truly-catalytic Au-polymer composite by assembling ultrasmall Au-nanoparticles at the protein-repelling outer layer of a co-polymer scaffold via electrostatic loading. Illustrating the in vivo-compatibility of the novel catalysts, we show their capacity to uncage the anxiolytic agent fluoxetine at the central nervous system (CNS) of developing zebrafish, influencing their swim pattern. This bioorthogonal strategy has enabled -for the first time- modification of cognitive activity by releasing a neuroactive agent directly in the brain of an animal.     

Complex quasiparticle band structure induced by electron-phonon interaction: band splitting in the 1x1H/W110 surface

We show that the self-consistent solution of the complex Dyson equation for the electron-phonon (EP) problem introduces many body effects which are often observed in photoemission experiments. The formalism is applied to the H covered W(110) surface, using first-principles results for the electronic and vibrational structure. We demonstrate that the measured spin-polarized surface band splitting [Phys. Rev. Lett. 84, 2925 (2000)10.1103/PhysRevLett.84.2925; 89, 216802 (2002)] can be traced back to different quasiparticle (QP) states induced by EP coupling. Despite the breakdown of the single QP picture, the spectral functions are very well represented by the predicted multiple QP structure.