A fundamental parameters approach including scattered radiation for mono-energetically excited samples in energy-dispersive x-ray fluorescence spectrometry

A fundamental parameters approach that incorporates data on scattered radiation is shown to be a useful tool for the determination of trace elements in light matrices. For thick, transparent samples, a computer program is developed that uses differetial intensity equations adjusted for decreasing geometric efficiency. Various organic and biological reference materials are analysed to assess the reliability of the procedure. A nested design for analysis of variance shows that major errors can originate from the deconvolution process and sample inhomogeneities in many cases. For loose powders, great care must be exercised to avoid errors caused by scatter from the sample cups. The program is also useful for alloys.     

Retention effects of oxidized polyphenols during analytical extraction of phenolic compounds of virgin olive oil

The hydrophilic extract of virgin olive oil contains several phenolic compounds such as simple phenols, lignans, and secoiridoids that have been widely studied in recent years. Interest in the hydrophilic extract has also been extended to the fraction of oxidized phenols that form during storage as a consequence of oxidative stress. The present investigation compares the two most commonly used extraction methods, namely liquid-liquid extraction and SPE, on fresh virgin olive oil and that kept at different temperatures in the presence of oxygen to promote the formation of oxidative products. The selective retention of these natural and oxidized phenolic compounds in relation to the extraction method was assessed. Quantification of eight identified phenolic molecules and 11 unknown peaks was performed by HPLC-DAD/MSD.     

The role of the atomic charges on the ligands and platinum(II) in affecting the cis and trans influences in [PtXL(PPh3)2]+ complexes (X = NO3, Cl, Br, I; L = 4-substituted pyridines, amines, PPh3). A 31P NMR and DFT investigation

One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the anionic ligands X decrease along the same sequence I > Br > Cl > NO(3), as previously found for [PtX(PPh(3))(3)](+) (X = NO(3), Cl, Br, I, 3a-d), however in 4a-d the cis influence turns out to be more important than the trans. On the contrary, in [PtCl(4-Z-py)(PPh(3))(2)](+) (4b,e-k) the sequence of the trans influence of the 4-Z-pyridines is opposite to that of the cis, the latter being Z = CN > CHO > Br > PhCO > H > Me > (t)Bu > NH(2), i.e. the most basic pyridine gives rise to the lowest cis influence. This correlation was found to hold also for complexes 5a-c (L = amines). All the observed trends have been fully reproduced by B3LYP/def2-SVP DFT calculations, by looking at the relevant optimized bond lengths of selected complexes of type 3, 4 and 5. Subsequent evaluation of the atomic charges, by resorting to two independent methods, i.e., the Natural Bond Order analysis of the wavefunction and the Bader's Quantum Theory of Atoms in Molecules, allowed for rationalization of the origin of the cis and trans influences. The negative charge on the nitrogen atoms of free pyridines becomes more negative upon protonation and even more so when coordinated to the [PtCl(PPh(3))(2)](+) moiety. The least negatively charged nitrogen atom of coordinated pyridines is that of 4-CN-py (the highest cis influencing pyridine derivative), which gives rise to the lowest positive charge on Pt, confirming the relationship between the lowering of the charge on the metal ion and a high cis influence. The trans influence can be described in terms of competition between the charges on the two trans donor atoms. In contrast with the behaviour of pyridines, the positive charge on the phosphorous atom of free PPh(3) increases upon coordination to Pt(II), moreover the PPh(3) ligands acquire a substantial positive charge, thus efficiently delocalising the charge of the cationic complex.     

Understanding binding affinity: a combined isothermal titration calorimetry/molecular dynamics study of the binding of a series of hydrophobically modified benzamidinium chloride inhibitors to trypsin

The binding of a series of p-alkylbenzamidinium chloride inhibitors to the serine proteinase trypsin over a range of temperatures has been studied using isothermal titration (micro)calorimetry and molecular dynamics simulation techniques. The inhibitors have small structural variations at the para position of the benzamidinium ion. They show small differences in relative binding affinity but large compensating differences in enthalpy and entropy. Binding affinity decreases with increased branching at the first carbon but increases with increasing the length of a linear alkyl substituent, suggesting that steric hindrance and hydrophobic interactions play dominant roles in binding. Structural analysis showed that the backbone of the enzyme was unaffected by the change of the para substituent. In addition, binding does not correlate strongly with octanol/water partition data. To further characterize this system, the change in the heat capacity on binding, the change in solvent-accessible surface area on binding, the effect of inhibitor binding on the hydration of the active site, the pK(a) of His57, and interactions within the catalytic triad have been investigated. Although the changes in inhibitor structure are small, it is demonstrated that simple concepts such as steric hindrance, hydrophobicity, and buried surface area are insufficient to explain the binding data. Other factors, such as access to the binding site and the cost of dehydration of the active site, are of equal or greater importance.     

A Linear Ion Trap with an Expanded Inscribed Diameter to Improve Optical Access for Fluorescence Spectroscopy

We report a custom-geometry linear ion trap designed for fluorescence spectroscopy of gas-phase ions at ambient to cryogenic temperatures. Laser-induced fluorescence from trapped ions is collected from between the trapping rods, orthogonal to the excitation laser that runs along the axis of the linear ion trap. To increase optical access to the ion cloud, the diameter of the round trapping rods is 80% of the inscribed diameter, rather than the roughly 110% used to approximate purely quadrupolar electric fields. To encompass as much of the ion cloud as possible, the first collection optic has a 25.4 mm diameter and a numerical aperture of 0.6. The choice of geometry and collection optics yields 10⁷ detected photons/s from trapped rhodamine 6G ions. The trap is coupled to a closed-cycle helium refrigerator, which in combination with two 50 Ohm heaters enables temperature control to below 25 K on the rod electrodes. The purpose of the instrument is to broaden the applicability of fluorescence spectroscopy of gas-phase ions to cases where photon emission is a minority relaxation pathway. Such studies are important to understand how the microenvironment of a chromophore influences excited state charge transfer processes.

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Analytical performance characteristics of thin and thick film amperometric microcells

The analytical performance of amperometric microcells with different electrode geometries is compared for enzyme activity measurements. The microcells were fabricated with thin film photolithography or thick film screen-printing in four different designs. The cells made with the thin film process used flexible substrate with microelectrode array or a circular, disk-shaped working electrode. The screen-printed working electrodes had semicircle or disk shape on ceramic chips. Putrescine oxidase (PUO) activity measurement was used as a model. The determination of PUO activity is important in the clinical diagnosis of premature rupture of the amniotic membrane. An electropolymerized m-phenylenediamine size-exclusion layer was used to eliminate common interferences. The size exclusion layer revealed also to be advantageous in protecting the electrodes from fouling by putrescine (enzyme substrate). The electrode fouling of bare electrodes was insignificant for screen-printed electrodes, but very severe for electroplated platinum working electrodes. The microelectrode array electrodes demonstrated smaller RSD and higher normalized sensitivities for hydrogen peroxide and PUO activity. All the other electrodes were demonstrating comparable analytical performances.     

Theoretical studies of homogeneous catalysts mimicking nitrogenase

The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen 'fixation' via an iron molybdenum cofactor (FeMo-co) under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N? to various degrees. However, to date Mo(N?)(HIPTN)?N with (HIPTN)?N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N?. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.