Synthesis and characterization of a chromium(V) cis-dioxo bis(1,10-phenanthroline) complex and crystal and molecular structures of its chromium(III) precursor

The first structurally characterized Cr(V) dioxo complex, cis-[CrV(O)2(phen)2](BF4) (2, phen=1,10-phenanthroline) has been synthesized by the oxidation of a related Cr(III) complex, cis-[Cr(III)(phen)2(OH2)2](NO3)3.2.5H2O (1, characterized by X-ray crystallography), with NaOCl in aqueous solutions in the presence of excess NaBF4, and its purity has been confirmed by electrospray mass spectrometry (ESMS), EPR spectroscopy, and analytical techniques. Previously reported methods for the generation of Cr(V)-phen complexes, such as the oxidation of 1 with PbO2 or PhIO, have been shown by ESMS to lead to mixtures of Cr(III), Cr(V), Cr(VI), and in some cases Cr(IV) species, 3. Species 3 was assigned as [CrIV(O)(OH)(phen)2]+, based on ESMS and X-ray absorption spectroscopy measurements. A distorted octahedral structure for 2 (CrO, 1.63 A; Cr-N, 2.04 and 2.16 A) was established by multiple-scattering (MS) modeling of XAFS spectra (solid, 10 K). The validity of the model was verified by a good agreement between the results of MS XAFS fitting and X-ray crystallography for 1 (distorted octahedron; Cr-O, 1.95 A; Cr-N, 2.06 A). Unlike for the well-studied Cr(V) 2-hydroxycarboxylato complexes, 2 was equally or more stable in aqueous media (hours at pH=1-13 and 25 degrees C) compared with polar aprotic solvents. A stable Cr(III)-Cr(VI) dimer, [Cr(III)(Cr(VI)O4)(phen)2]+ (detected by ESMS), is formed during the decomposition of 2 in nonaqueous media. Comparative studies of the oxidation of 1 by NaOCl or PbO2 have shown that [Cr(V)(O)2(phen)2]+ was the active species responsible for the previously reported oxidative DNA damage, bacterial mutagenicity, and increased incidence of micronuclei in mammalian cells, caused by the oxidation products of 1 with PbO2. Efficient oxidation of 1 to a genotoxic species, [Cr(V)(O)2(phen)2]+, in neutral aqueous media by a biological oxidant, hypochlorite, supports the hypothesis on a significant role of reoxidation of Cr(III) complexes, formed during the intracellular reduction of Cr(VI), in Cr(VI)-induced carcinogenicity. Similar oxidation reactions may contribute to the reported adverse effects of a popular nutritional supplement, Cr(III) picolinate.     

Identification of sildenafil,tadalafil and vardenafil by gas chromatography–mass spectrometry on short capillary column

Sildenafil and its analogues (tadalafil and vardenafil) are phosphodiesterase type 5 inhibitors used in the treatment of male erectile dysfunction. Some dietary supplements, herbal preparations and food products which claim to enhance male sexual function have been found to be adulterated with these drugs. In this study, a gas chromatograph–mass spectrometer (GC–MS) assay was developed for identification of the drugs. In addition to good and short chromatographic separation that can be achieved within 6 min by using a short 10 m capillary column, no prior sample clean-up before GC–MS analysis was required, thus making this assay a cost saving and rapid method. Furthermore, the assay is specific as the identification of sildenafil, tadalafil and vardenafil were done by detection of molecular ions; m/z 474, 389 and 448, respectively, and several other characteristic ions resulted from the mass fragmentation of individual molecules. Using our currently developed assay, sildenafil and its analogues were successfully identified in food and herbal matrices.     

Biomedical applications of X-ray absorption and vibrational spectroscopic microscopies in obtaining structural information from complex systems

Protein crystallography and NMR spectroscopy took decades to emerge as routine techniques in structural biology. X-ray absorption spectroscopy now has reached a similar stage of maturity for obtaining complementary local structural information around metals in metalloproteins. However, the relatively recent emergence of X-ray and vibrational spectroscopic microprobes that build on these techniques has enabled the structural information obtained from the “mature” techniques on isolated biomolecules to be translated into in situ structural information from inhomogeneous complex systems, such as whole cells and tissues.     

Experimental factors affecting the quality and reproducibility of MALDI TOF mass spectra obtained from whole bacteria cells

Numerous experimental factors are shown to significantly influence the spectra obtained when bacteria are analyzed by MALDI TOF/MS. Detailed investigation of the instrument parameters and sample preparation are all shown to influence the spectra. Of these, the preanalysis sample preparation steps incorporate the most important elements influencing the quality and reproducibility of the spectra. Some of the most important sample preparation factors include the method employed for sterilization, the type of matrix, the matrix solvent and concentration of cells in the matrix, as well as the type and concentration of acid added to the matrix. The effects of these parameters, as well as other aspects of sample preparation and the effects of several instrumental parameters on spectra are presented. Optimization and control of all experimental variables leads to a stable protocol for analysis of bacteria. The protocol employs a Nd:Yag laser and describes both sample handling and instrument conditions which consistently yield reproducible MALDI TOF mass spectra with greater than 25 peaks from both gram-positive and gram-negative bacteria.     

Ionic liquid matrix-induced metastable decay of peptides and oligonucleotides and stabilization of phospholipids in MALDI FTMS analyses

Room-temperature ionic liquid matrices (ILMs) have recently been investigated for use in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) and proven to be advantageous. Literature accounts of ILM performance for biological samples document increased sensitivity and ionization efficiency. These claims have been investigated here, and are supported for MALDI TOF applications to peptides, oligonucleotides, and phospholipids. Peptides and oligonucleotides however, do not behave in the same way when ILMs are used for MALDI FTMS. As reported here, with 3 tesla MALDI FTMS peptides and oligonucleotides fragment readily. These observations contrast with those found for MALDI time-of-flight mass spectrometry. Fragmentation is apparently slower than the time required to accelerate ions in a MALDI TOF mass spectrometer, but is readily observed by MALDI FTMS. Therefore, fragmentation of these molecules must occur on a relatively slow time scale. As trapping time is extended, increased fragmentation of peptides and oligonucleotides is seen. However, phospholipids do not fragment extensively. Furthermore, use of traditional solid matrices causes significant fragmentation for this category of compound but is suppressed by use of ILMs.     

Robust global exponential synchronization of general Lur’e chaotic systems subject to impulsive disturbances and time delays

In this paper, we aim to study the robust global exponential synchronization problem for a general class of Lur’e chaotic systems subject to time delays and impulsive disturbances. Furthermore, we also provide an estimation of the maximum Lyapunov exponent. By using the Lyapunov function method and linear matrix inequality (LMI) technique, sufficient conditions for the robust global exponential synchronization and estimation of its maximum Lyapunov exponent are obtained for the class of Lur’e chaotic systems with and without time delays, respectively. Furthermore, by applying the M-matrix theory, some of these sufficient conditions are shown to be expressible in forms of fairly simple algebraic conditions. For illustration, several examples are solved by using the sufficient conditions obtained.     

An Exact Penalty Method for Free Terminal Time Optimal Control Problem with Continuous Inequality Constraints

In this paper, we consider a class of optimal control problems with free terminal time and continuous inequality constraints. First, the problem is approximated by representing the control function as a piecewise-constant function. Then the continuous inequality constraints are transformed into terminal equality constraints for an auxiliary differential system. After these two steps, we transform the constrained optimization problem into a penalized problem with only box constraints on the decision variables using a novel exact penalty function. This penalized problem is then solved by a gradient-based optimization technique. Theoretical analysis proves that this penalty function has continuous derivatives, and for a sufficiently large and finite penalty parameter, its local minimizer is feasible in the sense that the continuous inequality constraints are satisfied. Furthermore, this local minimizer is also the local minimizer of the constrained problem. Numerical simulations on the range maximization for a hypersonic vehicle reentering the atmosphere subject to a heating constraint demonstrate the effectiveness of our method.     

An Exact Penalty Function Method for Continuous Inequality Constrained Optimal Control Problem

In this paper, we consider a class of optimal control problems subject to equality terminal state constraints and continuous state and control inequality constraints. By using the control parametrization technique and a time scaling transformation, the constrained optimal control problem is approximated by a sequence of optimal parameter selection problems with equality terminal state constraints and continuous state inequality constraints. Each of these constrained optimal parameter selection problems can be regarded as an optimization problem subject to equality constraints and continuous inequality constraints. On this basis, an exact penalty function method is used to devise a computational method to solve these optimization problems with equality constraints and continuous inequality constraints. The main idea is to augment the exact penalty function constructed from the equality constraints and continuous inequality constraints to the objective function, forming a new one. This gives rise to a sequence of unconstrained optimization problems. It is shown that, for sufficiently large penalty parameter value, any local minimizer of the unconstrained optimization problem is a local minimizer of the optimization problem with equality constraints and continuous inequality constraints. The convergent properties of the optimal parameter selection problems with equality constraints and continuous inequality constraints to the original optimal control problem are also discussed. For illustration, three examples are solved showing the effectiveness and applicability of the approach proposed.