Site-selective aqueous C–H acylation of tyrosine-containing oligopeptides with aldehydes

The development of useful synthetic tools to label amino acids within a peptide framework for the ultimate modification of proteins in a late-stage fashion is a challenging task of utmost importance within chemical biology. Herein, we report the first Pd-catalyzed C–H acylation of a collection of Tyr-containing peptides with aldehydes. This water-compatible tagging technique is distinguished by its site-specificity, scalability and full tolerance of sensitive functional groups. Remarkably, it provides straightforward access to a high number of oligopeptides with altered side-chain topology including mimetics of endomorphin-2 and neuromedin N, thus illustrating its promising perspectives toward the diversification of structurally complex peptides and chemical ligation.

A novel Pd-catalyzed C–H acylation reaction with readily available aldehydes under an aqueous environment towards the assembly of non-protegenic acylated Tyr-containing oligopeptides is presented.     

Ion larmour radius effect on rf ponderomotive forces and induced poloidal flow in tokamak plasmas

Analytical approximations are used to clarify the effect of Larmour radius on rf ponderomotive forces and on poloidal flows induced by them in tokamak plasmas. The electromagnetic force is expressed as a sum of a gradient part and of a wave momentum transfer force, which is proportional to wave dissipation. The first part, called the gradient electromagnetic stress force, is combined with fluid dynamic (Reynolds) stress force, and gyroviscosity is included into viscosity force to model finite ion Larmour radius effects in the momentum response to the rf fields in plasmas. The expressions for the relative magnitude of different forces for kinetic Alfven waves and fast waves are derived.     

On-line renewable solid-phase extraction hyphenated to liquid chromatography for the determination of UV filters using bead injection and multisyringe-lab-on-valve approach

For the first time, an automatic sample pre-treatment/detection method is proposed for the multiclass determination of UV filters (namely, benzophenone-3, ethylhexylmetoxycinnamate, butylmethoxydibenzoylmethane and homosalate) in environmental samples. The new methodology comprises in-line solid-phase extraction (SPE) of the target analytes by exploiting the bead injection (BI) concept in a mesofluidic lab-on-valve (LOV) format, with subsequent determination by liquid chromatography (LC). The proposed microanalytical system, using a multisyringe burette as propulsion unit, automatically performed the overall SPE steps, including the renewal of the sorbent in each analytical cycle to prevent sample cross-contamination and the post-extraction adjustment of the eluate composition to prevent chromatographic band broadening effects. In order to expedite the LC separation, a C₁₈ monolithic column was applied and an accelerated isocratic elution was carried out by using a cationic surfactant as mobile phase additive. The LOV-BI-LC method was proven reliable for handling and analysis of complex matrices, e.g., spiked swimming pool water and seawater, with limits of detection ranging between 0.45 and 3.2 μg L⁻¹ for 9 mL sample volume. Linear calibration was attained up to 160 μg L⁻¹ for homosalate and up to 35 μg L⁻¹ for the other target analytes, with good reproducibility (RSD < 13%, for 5 different SPE columns). The hyphenated scheme is able to process a given sample simultaneously and within the same time frame than the chromatographic separation/determination of the formerly pre-treated sample, providing concentration values every 9 min. Hence, the sample throughput was enhanced up to 33 times when compared with previously reported off-line SPE methods. A drastic reduction in reagent consumption and effluent production was also attained, contributing to the development of an environment-friendly analyzer.     

Enzyme based assays in a sequential injection format: a review

Sequential injection analysis systems have been extensively exploited in the last decades for the implementation of enzyme based assays aiming the evaluation of enzyme activity or the determination of specific analytes. The most prominent aspects of the automation of enzymatic assays in these systems are discussed in this review. Special attention is devoted to the mode of enzyme manipulation in homogeneous or heterogeneous media and to the comparison with batch and flow injection enzyme methodologies. The possibility of implementing strategies for the enhancement of selectivity in specific determinations is also addressed. The more recent trends in this field are discussed focusing mainly on the miniaturization resorting to the lab-on valve platform as well as on the bead injection concept.     

The relative isotopic abundance (δ13C, δ15N) during composting of agricultural wastes in relation to compost quality and feedstock

Variations in the relative isotopic abundance of C and N (δ¹³C and δ¹⁵N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure?+?legume residues; dairy manure?+?jatropha mill cake; dairy manure?+?sugarcane residues; dairy manure alone) were used for aerobic–thermophilic composting. No significant differences were found between the δ¹³C values of the feedstock and the final compost, except for dairy manure?+?sugarcane residues (from initial ratio of ?13.6?±?0.2?‰ to final ratio of ?14.4?±?0.2?‰). δ¹⁵N values increased significantly in composts of horse bedding manure?+?legumes residues (from initial ratio of +5.9?±?0.1?‰ to final ratio of +8.2?±?0.5?‰) and dairy manure?+?jatropha mill cake (from initial ratio of +9.5?±?0.2?‰ to final ratio of +12.8?±?0.7?‰) and was related to the total N loss (mass balance). δ¹³C can be used to differentiate composts from different feedstock (e.g. C₃ or C₄ sources). The quantitative relationship between N loss and δ¹⁵N variation should be determined.     

Reductive Elimination at Pb(II) Center of an (Amino)plumbylene-Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis

A stable (amino)plumbylene-substituted phosphaketene 3 was synthesized by the successive reactions of PbCl₂ with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3 , at 80 °C, leads to the transient formation of corresponding amino- and phosphanylidene-phosphaketenes ( 6 and 7 ), via a reductive elimination at the Pb^II center forming new N−P and P−P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4 , which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.     

On quantum stability for systems under quasiperiodic perturbations

We prove that the spectrum defined in terms of the autocorrelation function of a harmonic subject to a quasiperiodic perturbation, is, at resonance, transient absolutely continuous, covering the whole line. In the nonresonant case, and under some supplementary Diophantine condition, it is pure point, coinciding with the spectrum of a special almost-periodic function.     

Flow-through solid-phase reflectometric method for simultaneous multiresidue determination of nitrophenol derivatives

In this paper, a flow-through optosensor based on diffuse reflectance spectroscopy and multivariate regression modelling is proposed for simultaneous multiresidue determination of trace level concentrations of nitro-substituted phenols. The optrode integrates on-line anion-exchange sorptive preconcentration and matrix removal with direct detection of sorbed species onto the sensing layer and chemometric deconvolution of overlapped spectra. After recording of the reflectometric spectrum, fast chemosensor regeneration is accomplished with an acidic methanolic eluent followed by a metered volume of alkaline solution. The full automation of the analytical procedure is ensured by flow-programming as executed via a software-controlled multisyringe pump and a set of multiposition and solenoid valves.

Under the optimized chemical and physical variables, the 3σ_blank detection limits for 2-, and 4-nitrophenol and 2,4-dinitrophenol were 0.69, 0.42 and 0.37 μg L⁻¹, respectively, for a sample loading volume of 4.0 mL with enrichment factors of 73, 74 and 81, respectively, and repeatability better than 3.0%. The analytical applicability of the optosensing system was asserted by the satisfactory results attained in its application to monitoring of nitrophenol derivatives in spiked environmental waters including highly saline matrices via the standard additions method.     

New decision rules for exact search in N-Queens

This paper presents a set of new decision rules for exact search in N-Queens. Apart from new tiebreaking strategies for value and variable ordering, we introduce the notion of ‘free diagonal’ for decision taking at each step of the search. With the proposed new decision heuristic the number of subproblems needed to enumerate the first K solutions (typically K = 1, 10 and 100) is greatly reduced w.r.t. other algorithms and constitutes empirical evidence that the average solution density (or its inverse, the number of subproblems per solution) remains constant independent of N. Specifically finding a valid configuration was backtrack free in 994 cases out of 1,000, an almost perfect decision ratio. This research is part of a bigger project which aims at deriving new decision rules for CSP domains by evaluating, at each step, a constraint value graph G _c . N-Queens has adapted well to this strategy: domain independent rules are inferred directly from G _c whereas domain dependent knowledge is represented by an induced hypergraph over G _c and computed by similar domain independent techniques. Prior work on the Number Place problem also yielded similar encouraging results.