Iridium catalyzed alkylation of 2′-hydroxyacetophenone with alcohols under thermal or microwave conditions

2′-Hydroxyacetophenone was alkylated with a range of substituted benzyl and heteroaryl alcohols to afford the corresponding C-alkylated products in good yields under microwave irradiation. The C-alkylated products were reacted with bromoacetonitrile to afford 2-amino-3-benzyl 1,4-naphthoquinone derivatives in moderate yields.     

The use of carbon dioxide as the reaction cell gas for the separation of uranium and plutonium in quadrupole inductively coupled plasma mass spectrometry (ICP-MS) for nuclear forensic samples

²²⁶Ra, ²³⁸U, ²³²Th, and ⁴⁰K radionuclides have been determined using gamma-ray spectrometry in soil samples collected from urban areas in the southern governorates of Jordan and showed average concentrations of (39 ± 18), (45 ± 20), (23 ± 13), and (233 ± 128) Bq kg^?1, respectively. The corresponding radio-elemental concentrations in the existing geological features were obtained and examined for the relative depletion/enrichment processes and state of equilibrium in soils. Radium equivalent activity, hazard indices, and annual gonadal dose equivalent do not exceed the permissible limits. Absorbed dose rates in air outdoor and external effective dose showed average values of 44.0 nGy h^?1 and 54.4 μSv y^?1, respectively.     

Mass Spectral Detection of Forward- and Reverse-Hydrogen/Deuterium Exchange Resulting from Residual Solvent Vapors in Electrospray Sources

Characterizing glycans is analytically challenging since glycans are heterogeneous, branched polymers with different three-dimensional conformations. Hydrogen/deuterium exchange-mass spectrometry (HDX-MS) has been used to analyze native conformations and dynamics of biomolecules by measuring the mass increase of analytes as labile protons are replaced with deuterium following exposure to deuterated solvents. The rate of exchange is dependent on the chemical functional group, the presence of hydrogen bonds, pH, temperature, charge, and solvent accessibility. HDX-MS of carbohydrates is challenging due to the rapid exchange rate of hydroxyls. Here, we describe an observed HDX reaction associated with residual solvent vapors saturating electrospray sources. When undeuterated melezitose was infused after infusing D₂O, samples with up to 73% deuterium exchange were detected. This residual solvent HDX was observed for both carbohydrates and peptides in multiple instruments and dependent on sample infusion rate, infusion time, and deuterium content of the solvent. This residual solvent HDX was observed over several minutes of sample analysis and persisted long enough to alter the measured deuterium labeling and possibly change the interpretation of the results. This work illustrates that residual solvent HDX competes with in-solution HDX for rapidly exchanging functional groups. Thus, we propose conditions to minimize this effect, specifically for top-down, in-electrospray ionization, and quench-flow HDX experiments.

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Exchange repulsion between effective fragment potentials and ab initio molecules

The exchange repulsion energy and the Fock operator for systems that contain both effective fragment potentials and ab initio molecules have been derived, implemented, and tested on six mixed dimers of common solvent molecules. The implementation requires a balance between accuracy and computational efficiency. The gradient of the exchange repulsion has also been derived. Computational timings and the current challenges facing the implementation of the gradient are discussed.     

The sonochemical coating of cotton withstands 65 washing cycles at hospital washing standards and retains its antibacterial properties

Hospital-acquired nosocomial infections are a major health, and consequently financial issue, in the world healthcare system. The problem of bacterial infections in general, and in hospitals in particular, has led to extensive scientific and industrial efforts to fabricate antibacterial textiles. A sonochemical coating machine was developed and built and its ability to coat antibacterial nanoparticles (NPs) onto 40–50 meter length of materials on a roll to roll basis at a speed of 22 cm/min. Cotton coated sonochemically with copper oxide nanoparticles (CuO NPs) was found to maintain its antibacterial properties even after 65 cycles of washings according to hospital protocols of hygienic washing (75 °C). This demonstrates the good quality and high stability of this sonochemically produced NPs coating on textiles. Durable antibacterial textiles such as these may be suitable for wide spread use in future hospital environments where hygiene control is of paramount importance.     

Structural and magnetic behavior of the kinked chain Cu(hfac)2(tan) and its relevance to Cu(NO3)2(tan) (hfac = hexafluoroacetylacetonate; tan = 1,4,5-triazanaphthalene)

When stoichiometric amounts of Cu(hfac)(2).H(2)O and 1,4,5-triazanaphthalene (tan) were combined in methanol, green crystals of Cu(hfac)(2)(tan) were formed. Its structure was determined at low temperature (P2(1)/c; a = 8.3308(4) A, b = 14.8945(7) A, c = 18.3046(10) A, beta = 99.298(2) degrees, V = 2241.5(3) A(3)) and found to consist of a novel kinked-chain arrangement where N atoms on opposite sides of the tan ligand bridge Cu(hfac)(2) moieties together. Long axial Cu-N bonds lead to rather weak (J/k(B) = -0.06(5) K) antiferromagnetic interactions according to a Bonner-Fisher fit of the magnetic susceptibility data. The magnetic behavior demonstrated by Cu(hfac)(2)(tan) contrasts markedly with that of Cu(NO(3))(2)(tan), as reported by Hatfield and co-workers, and is attributed to the differing orientations of the Cu d(x)2(-)(y)2 magnetic orbital.     

A General and Air‐tolerant Strategy to Conjugated Polymers within Seconds under Palladium(I) Dimer Catalysis

While current M⁰/M^II based polymerization strategies largely focus on fine‐tuning the catalyst, reagents and conditions for each and every monomer, this report discloses a single method that allows access to a variety of different conjugated polymers within seconds at room temperature. Key to this privileged reactivity is an air‐ and moisture stable dinuclear Pd^I catalyst. The method is operationally simple, robust and tolerant to air.     

Formation of N719 dye multilayers on dye sensitized solar cell photoelectrode surfaces investigated by direct determination of element concentration depth profiles

The structure of the dye layer adsorbed on the titania substrate in a dye-sensitized solar cell is of fundamental importance for the function of the cell, since it strongly influences the injection of photoelectrons from the excited dye molecules into the titania substrate. The adsorption isotherms of the N719 ruthenium-based dye were determined both with a direct method using the depth profiling technique neutral impact collision ion scattering spectroscopy (NICISS) and with the standard indirect solution depletion method. It is found that the dye layer adsorbed on the titania surface is laterally inhomogeneous in thickness and there is a growth mechanism already from low coverage levels involving a combination of monolayers and multilayers. It is also found that the amount of N719 adsorbed on the substrate depends on the titania structure. The present results show that dye molecules in dye-sensitized solar cells are not necessarily, as presumed, adsorbed as a self-assembled monolayer on the substrate.     

Quartz Crystal Microbalance Analysis of DNA-Templated Calcium Phosphate Mineralization

A quartz crystal microbalance (QCM) sensor was developed for the quantitation of calcium phosphate mineralization and the assessment of DNA as a template molecule. Inherent advantages of QCM, such as nanogram sensitivity, temporal resolution, surface-based measurements, and flow capabilities, were leveraged in the design of this sensor, and in-line fluidic mixing was used to control precursor reaction. This research shows that DNA, a highly programmable anionic polymer, is able to template and control mineralization of calcium phosphate, with nucleation occurring in less than 15 min and initial rates ranging from 4 to 8 ng/min. FT-IR measurements show mineralized material to be calcium phosphate resembling hydroxyapatite (HAP) when a DNA template is used. DNA is a promising mineralization template, and the QCM proves to be a dynamic technique for a broad range of heterogeneous mineralization experiments in complement to classic, diffusion-limited, end-point analysis techniques.     

Virtual screening using a conformationally flexible target protein: models for ligand binding to p38α MAPK

We have used virtual screening to develop models for the binding of aryl substituted heterocycles to p38α MAPK. Virtual screening was conducted on a number of p38α MAPK crystal structures using a library of 46 known p38α MAPK inhibitors containing a heterocyclic core substituted by pyridine and fluorophenyl rings (structurally related to SB203580) and a set of decoy compounds. Multiple protonation states and tautomers of active and decoy compounds were considered. Each docking model was evaluated using receiver operating characteristic (ROC) curves and enrichment factors. The two best performing single crystal structures were found to be 1BL7 and 2EWA, with enrichment factors of 14.1 and 13.0 at 2 % of the virtual screen respectively. Ensembles of up to four receptors of similar conformations were generated, generally giving good or very good performances with high ROC AUCs and good enrichment. The 1BL7-2EWA ensemble was able to outperform each of its constituent receptors and gave high enrichment factors of 17.3, 12.0, 8.0 at 2, 5 and 10 % respectively, of the virtual screen. A ROC AUC of 0.94 was obtained for this ensemble. This method may be applied to other proteins where there are a large number of inhibitor classes with different binding site conformations.