Modulating Weak Interactions for Molecular Recognition: A Dynamic Combinatorial Analysis for Assessing the Contribution of Electrostatics to the Stability of CH–π Bonds in Water

Electrostatic and charge‐transfer contributions to CH–π complexes can be modulated by attaching electron‐withdrawing substituents to the carbon atom. While clearly stabilizing in the gas phase, the outcome of this chemical modification in water is more difficult to predict. Herein we provide a definitive and quantitative answer to this question employing a simple strategy based on dynamic combinatorial chemistry.     

Reversible microwave-assisted cycloaddition of aziridines to carbon nanotubes

We report a new approach that uses microwaves to rapidly functionalize carbon nanotubes by using 1,3-dipolar cycloaddition of aziridines, well-known precursors to azomethine ylides, in solvent-free conditions. The efficiency of our microwave-mediated protocol is confirmed by comparison to a similar protocol in classical conditions for the azomethine ylides in DMF. Under these latter conditions, the reaction proceeds in 5 days (against 1 h under microwave irradiation), and the functionalization degree is much lower, as confirmed by thermogravimetric analysis and Raman spectroscopy. With our procedure, we easily scale-up the reaction up to 250 mg of functionalized MWNT in 1 h. We also provide an indirect proof of the covalent sidewall functionalization of the tubes.     

Improved protein identification efficiency by mass spectrometry using N-terminal chemical derivatization of peptides from Angiostrongylus costaricensis, a nematode with unknown genome

Matrix-assisted laser desorption ionization (MALDI), Peptide Mass Fingerprinting (PMF) and MALDI-MS/MS ion search (using MASCOT) have become the preferred methods for high-throughput identification of proteins. Unfortunately, PMF can be ambiguous, mainly when the genome of the organism under investigation is unknown and the quality of spectra generated is poor and does not allow confident identification. The post-source decay (PSD) fragmentation of singly charged tryptic peptide ions generated by MALDI-TOF/TOF typically results in low fragmentation efficiency and/or complex spectra, including backbone fragmentation ions (series b and y), internal fragmentation etc. Interpreting these data either manually and/or using de novo sequencing software can frequently be a challenge. To overcome this limitation when studying the proteome of adult Angiostrongylus costaricensis, a nematode with unknown genome, we have used chemical N-terminal derivatization of the tryptic peptides with 4-sulfophenyl isothiocyanate (SPITC) prior to MALDI-TOF/TOF MS. This methodology has recently been reported to enhance the quality of MALDI-TOF/TOF-PSD data, allowing the obtainment of complete sequence of most of the peptides and thus facilitating de novo peptide sequencing. Our approach, consisting of SPITC derivatization along with manual spectra interpretation and Blast analysis, was able to positively identify 76% of analyzed samples, whereas MASCOT analysis of derivatized samples, MASCOT analysis of nonderivatized samples and PMF of nonderivatized samples yielded only 35, 41 and 12% positive identifications, respectively. Moreover, de novo sequencing of SPITC modified peptides resulted in protein sequences not available in NCBInr database paving the way to the discovery of new protein molecules.     

Microwave-assisted reactions in heterocyclic compounds with applications in medicinal and supramolecular chemistry

Microwave irradiation has been successfully applied in organic chemistry. Spectacular accelerations, higher yields under milder reaction conditions and higher product purities have all been reported. Indeed, a number of authors have described success in reactions that do not occur under conventional heating and modifications in selectivity (chemo-, regio- and stereoselectivity) have even been reported. Recent advances in microwave-assisted combinatorial chemistry include high-speed solid-phase and polymer-supported organic synthesis, rapid parallel synthesis of compound libraries, and library generation by automated sequential microwave irradiation. In addition, new instrumentation for high-throughput microwave-assisted synthesis continues to be developed at a steady pace. The impressive speed combined with the unmatched control over reaction parameters justifies the growing interest in this application of microwave heating. In this review we highlight our recent advances in this area, with a particular emphasis on cycloaddition reactions of heterocyclic compounds both with and without supports, applications in supramolecular chemistry and the reproducibility and scalability of organic reactions involving the use of microwave irradiation techniques.     

An Assessment of Mass Flows,Removal and Environmental Emissions of Bisphenols in a Sequencing Batch Reactor Wastewater Treatment Plant

This study analyzed 16 bisphenols (BPs) in wastewater and sludge samples collected from different stages at a municipal wastewater treatment plant based on sequencing batch reactor technology. It also describes developing an analytical method for determining BPs in the solid phase of activated sludge based on solid-phase extraction and gas chromatography-mass spectrometry. Obtained concentrations are converted into mass flows, and the biodegradation of BPs and adsorption to primary and secondary sludge are determined. Ten of the sixteen BPs were present in the influent with concentrations up to 434 ng L⁻¹ (BPS). Only five BPs with concentrations up to 79 ng L⁻¹ (BPA) were determined in the plant effluent, accounting for 8 % of the total BPs determined in the influent. Eleven per cent of the total BPs were adsorbed on primary and secondary sludge. Overall, BPs biodegradation efficiency was 81%. The highest daily emissions via effluent release (1.48 g day⁻¹) and sludge disposal (4.63 g day⁻¹) were for BPA, while total emissions reached 2 g day⁻¹ via effluent and 6 g day⁻¹ via sludge disposal. The data show that the concentrations of BPs in sludge are not negligible, and their environmental emissions should be monitored and further studied.     

On the exact calculation of the fill rate in a periodic review inventory policy under discrete demand patterns

The primary goal of this paper is the development of a generalized method to compute the fill rate for any discrete demand distribution in a periodic review policy. The fill rate is defined as the fraction of demand that is satisfied directly from shelf. In the majority of related work, this service metric is computed by using what is known as the traditional approximation, which calculates the fill rate as the complement of the quotient between the expected unfulfilled demand and the expected demand per replenishment cycle, instead of focusing on the expected fraction of fulfilled demand. This paper shows the systematic underestimation of the fill rate when the traditional approximation is used, and revises both the foundations of the traditional approach and the definition of fill rate itself. As a result, this paper presents the following main contributions: (i) a new exact procedure to compute the traditional approximation for any discrete demand distribution; (ii) a more suitable definition of the fill rate in order to ignore those cycles without demand; and (iii) a new standard procedure to compute the fill rate that outperforms previous approaches, especially when the probability of zero demand is substantial. This paper focuses on the traditional periodic review, order up to level system under any uncorrelated, discrete and stationary demand pattern for the lost sales scenario.     

Removal of pharmaceuticals from wastewater by biological processes,hydrodynamic cavitation and UV treatment

To augment the removal of pharmaceuticals different conventional and alternative wastewater treatment processes and their combinations were investigated. We tested the efficiency of (1) two distinct laboratory scale biological processes: suspended activated sludge and attached-growth biomass, (2) a combined hydrodynamic cavitation–hydrogen peroxide process and (3) UV treatment. Five pharmaceuticals were chosen including ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac, and an active metabolite of the lipid regulating agent clofibric acid.Biological treatment efficiency was evaluated using lab-scale suspended activated sludge and moving bed biofilm flow-through reactors, which were operated under identical conditions in respect to hydraulic retention time, working volume, concentration of added pharmaceuticals and synthetic wastewater composition. The suspended activated sludge process showed poor and inconsistent removal of clofibric acid, carbamazepine and diclofenac, while ibuprofen, naproxen and ketoprofen yielded over 74% removal. Moving bed biofilm reactors were filled with two different types of carriers i.e. Kaldnes K1 and Mutag BioChip? and resulted in higher removal efficiencies for ibuprofen and diclofenac. Augmentation and consistency in the removal of diclofenac were observed in reactors using Mutag BioChip? carriers (85% ± 10%) compared to reactors using Kaldnes carriers and suspended activated sludge (74% ± 22% and 48% ± 19%, respectively). To enhance the removal of pharmaceuticals hydrodynamic cavitation with hydrogen peroxide process was evaluated and optimal conditions for removal were established regarding the duration of cavitation, amount of added hydrogen peroxide and initial pressure, all of which influence the efficiency of the process. Optimal parameters resulted in removal efficiencies between 3–70%. Coupling the attached-growth biomass biological treatment, hydrodynamic cavitation/hydrogen peroxide process and UV treatment resulted in removal efficiencies of >90% for clofibric acid and >98% for carbamazepine and diclofenac, while the remaining compounds were reduced to levels below the LOD. For ibuprofen, naproxen, ketoprofen and diclofenac the highest contribution to overall removal was attributed to biological treatment, for clofibric acid UV treatment was the most efficient, while for carbamazepine hydrodynamic cavitation/hydrogen peroxide process and UV treatment were equally efficient.     

On quintessential cosmological models and exponential potentials

We first study dark energy models with a minimally-coupled scalar field and generalized exponential potentials, admitting exact solutions for the cosmological equations: actually, it turns out that for this class of potentials the Einstein field equations exhibit alternative Lagrangians, and are completely integrable and separable. We analyze their analytical solutions, especially discussing when they are compatible with a late time quintessential expansion of the universe. As a further issue, we discuss how quintessential scalar fields with exponential potentials can be connected to the inflationary phase, building up a quintessential inflationary scenario: actually, it turns out that the transition from inflation toward late-time exponential quintessential tail admits a kination period, which is an indispensable ingredient of this kind of theoretical models. All such considerations have been made by including also radiation into the model.     

A three-point Taylor algorithm for three-point boundary value problems

We consider second-order linear differential equations φ(x)y^″+f(x)y^′+g(x)y=h(x) in the interval (−1,1) with Dirichlet, Neumann or mixed Dirichlet-Neumann boundary conditions given at three points of the interval: the two extreme points x=±1 and an interior point x=s∈(−1,1). We consider φ(x), f(x), g(x) and h(x) analytic in a Cassini disk with foci at x=±1 and x=s containing the interval [−1,1]. The three-point Taylor expansion of the solution y(x) at the extreme points ±1 and at x=s is used to give a criterion for the existence and uniqueness of the solution of the boundary value problem. This method is constructive and provides the three-point Taylor approximation of the solution when it exists. We give several examples to illustrate the application of this technique.