Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine

In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrochemical reduction of monothiobenzils in the presence of aroyl chlorides. First synthesis of (Z)-α-benzoyloxy-β-benzoylthiostilbenes

The first method for the synthesis of the title compounds has been established involving a stereoselective electrochemical diacylation process. The cathodic reductions of monothiobenzils in an aprotic medium, under constant potential, in the presence of twofold molecular amounts of aroyl chlorides provide previously unknown (Z)-α-benzoyloxy-β-benzoythiostilbenes in high to quantitative yields.     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Indexing text using the Ziv–Lempel trie

Let a text of u characters over an alphabet of size σ be compressible to n phrases by the LZ78 algorithm. We show how to build a data structure based on the Ziv–Lempel trie, called the LZ-index, that takes 4nlog₂n(1+o(1)) bits of space (that is, 4 times the entropy of the text for ergodic sources) and reports the R occurrences of a pattern of length m in worst case time O(m³logσ+(m+R)logn). We present a practical implementation of the LZ-index, which is faster than current alternatives when we take into consideration the time to report the positions or text contexts of the occurrences found.     

Practical algorithms for transposition-invariant string-matching

We consider the problems of (1) longest common subsequence (LCS) of two given strings in the case where the first may be shifted by some constant (that is, transposed) to match the second, and (2) transposition-invariant text searching using indel distance. These problems have applications in music comparison and retrieval. We introduce two novel techniques to solve these problems efficiently. The first is based on the branch and bound method, the second on bit-parallelism. Our branch and bound algorithm computes the longest common transposition-invariant subsequence (LCTS) in time O((m²+loglogσ)logσ) in the best case and O((m²+logσ)σ) in the worst case, where m and σ, respectively, are the length of the strings and the size of the alphabet. On the other hand, we show that the same problem can be solved by using bit-parallelism and thus obtain a speedup of O(w/logm) over the classical algorithms, where the computer word has w bits. The advantage of this latter algorithm over the present bit-parallel ones is that it allows the use of more complex distances, including general integer weights. Since our branch and bound method is very flexible, it can be further improved by combining it with other efficient algorithms such as our novel bit-parallel algorithm. We experiment on several combination possibilities and discuss which are the best settings for each of those combinations. Our algorithms are easily extended to other musically relevant cases, such as δ-matching and polyphony (where there are several parallel texts to be considered). We also show how our bit-parallel algorithm is adapted to text searching and illustrate its effectiveness in complex cases where the only known competing method is the use of brute force.     

The derivatives of equilibrium states

We find some estimates for the derivatives of equilibrium states of subshifts of finite type. We prove the differentiability (with respect to the potential) of integrals of certain discontinuous functions for the equilibrium state of a potential.research supported by CNPq, Brazil     

Risk-neutral valuation with infinitely many trading dates

The first Fundamental Theorem of Asset Pricing establishes the equivalence between the absence of arbitrage in financial markets and the existence of Equivalent Martingale Measures, if appropriate conditions hold. Since the theorem may fail when dealing with infinitely many trading dates, this paper draws on the A.A. Lyapunov Theorem in order to retrieve the equivalence for complete markets such that the Sharpe Ratio is adequately bounded.     

Practical aspects associated with location planning for maternal and perinatal assistance in Brazil

A study has been carried out aimed at reducing perinatal mortality in the municipality of Rio de Janeiro through a better distribution of health care facilities. The algorithmic aspects are detailed elsewhere and here the emphasis is on practical issues and difficulties encountered. A 3-level hierarchical model was developed. Both uncapacitated and capacitated versions are briefly described together with some results based on actual data. The project brought to light many contradictions between OR theory and practice in developing countries and, unfortunately, the models developed were not implemented by the municipality health authorities. Possible reasons for this outcome are analysed.     

Highly polarized dithiafulvenes: synthesis and nonlinear optical properties

Push-pull dithiafulvenes with reduced bond length alternation (BLA) and high optical nonlinearities have been prepared. The interplay between the proaromaticity of the donor and the structural and optical properties of these merocyanines is discussed. The donor ability of dithiafulvenes can reach that of ferrocene or dialkylaminophenyl groups.     

Polarization transforming properties of Dove prisms

We analyze the polarization changes introduced by a rotated Dove prism on the linearly polarized light, using the Jones calculus and the exact ray trace analysis. The state of polarization changes from the linear to a mildly elliptical one when a plane wave front passes through a rotated Dove prism: its semi-major axis is nearly parallel to the input plane of polarization, for any angle of prism rotation. The interferogram contrast remains high for all shearing angles in spite of polarization changes when the Dove prism is incorporated into a rotational shearing interferometer. These results are confirmed experimentally.