Thermodynamic temperature differences from the ITS-90 for the correction of thermodynamic property data

This paper purpose is to re-calculate thermodynamic or chemical–physical properties according to thermodynamic temperature T, where measured temperature values were obtained according to the ITS-90, T₉₀ (or the reverse). The main aims of the calculations are: to remove the discontinuity of the first derivative at 273.16 K that is intrinsic in the ITS-90 definition; to use a single cubic spline to model the database of the available experimental data over the whole temperature range (2.37 to 1235) K, while maximising the medium-range smoothness of the correction function; to compute corrections using only local polynomial coefficients.     

Light-directed radial combinatorial chemistry: orthogonal safety-catch protecting groups for the synthesis of small molecule microarrays

We describe the development of photolabile protecting groups based on the 3,4,5-trimethoxyphenacyl group (TMP). Orthogonal safety-catches were created by introducing an acid-activatible dimethyl ketal (AA-TMP) and an oxidatively activatible 1,3-dithiane (OA-TMP) into the photolabile TMP group. We demonstrate the application of these protecting groups in light-directed synthesis of small molecule microarrays with diversity elements radially attached to a hydroxyproline scaffold.     

Ozone monitoring in a Mediterranean forest using diffusive and continuous sampling

Ambient ozone was measured in a forest in Castelporziano (Italy) characterised by the prevailing presence of Holm-oak trees (Quercus ilex L.) from June to November 2003. Two methods for measuring ozone were used: long-term monitoring using diffusive samplers at three heights within the canopy, and continuous monitoring at two heights using the UV method. Results for one week mean ozone levels above and below the canopy from the diffusive samplers were compared to those obtained using the automatic analyser at the same levels. A good correlation between the two sampling techniques was found. Continuous monitoring showed a daily cycle with a midday maximum and a nocturnal minimum. While the forest floor consistently had the lowest ozone concentration, there were no differences during most daytime hours. The midday maximum is clearly due to downward mixing with O₃-rich air from above. The night-time ozone decay within the canopy is the result of dry deposition of O₃ and most likely due to reaction with biogenically produced NO. AOT40 within and above the canopy mostly exceeded the critical levels.     

Experiences in the measurement of RBC-bound IgG as markers of cell age

An immunologically mediated pathway has been largely accepted to be one of the mechanisms involved in the clearance of senescent or prematurely damaged RBC. According to this pathway, RBC removal is mediated by binding of naturally occurring IgG to clustered integral membrane proteins, followed by complement deposition. The validation of an immunoenzymatic method for the detection of RBC-bound autologous IgG is presented. The use of RBC-bound IgG as an index related to red cell age was evaluated by measuring IgG binding in RBC treated with the clustering agent ZnCl2, in density fractionated RBC and in a selected group of patients expected to have an altered RBC life span. The immunoenzymatic method for IgG detection resulted to be reproducible (CV = 3.4%). IgG binding to in vitro clustered RBC was found to be enhanced to a very great extent, about 20 times higher with respect to untreated RBC. A slight but significant increase (about 1.8-fold) in membrane-bound IgG was observed in the highest density fraction of normal RBC, which constituted 1% of the total cells. A significantly greater number of RBC-bound IgG was measured in splenectomized beta-thalassemia intermedia patients and in subjects with secondary decreases in the C3 complement fraction concentration.     

Spectrophotometric, EPR and kinetic characterisation of the >N-O* radical from 1-hydroxybenzotriazole, a key reactive species in mediated enzymatic oxidations

Characterisation of the aminoxyl (>N-O*) radical BTNO, generated from 1-hydroxybenzotriazole (HBT) by the one-electron oxidant CAN (a Ce(IV) salt), confirms BTNO as the reactive intermediate in oxidations run with the laccase/HBT system.     

Tunneling currents that increase with molecular elongation

We present a model molecular system with an unintuitive transport-extension behavior in which the tunneling current increases with forced molecular elongation. The molecule consists of two complementary aromatic units (1,4-anthracenedione and 1,4-anthracenediol) hinged via two ether chains and attached to gold electrodes through thiol-terminated alkenes. The transport properties of the molecule as it is mechanically elongated in a single-molecule pulling setting are computationally investigated using a combination of equilibrium molecular dynamics simulations of the pulling with gDFTB computations of the transport properties in the Landauer limit. Contrary to the usual exponential decay of tunneling currents with increasing molecular length, the simulations indicate that upon elongation electronic transport along the molecule increases 10-fold. The structural origin of this inverted trend in the transport is elucidated via a local current analysis that reveals the dual role played by H-bonds in both stabilizing π-stacking for selected extensions and introducing additional electronic couplings between the complementary aromatic rings that also enhance tunneling currents across the molecule. The simulations illustrate an inverted electromechanical single-molecule switch that is based on a novel class of transport-extension behavior that can be achieved via mechanical manipulation and highlight the remarkable sensitivity of conductance measurements to the molecular conformation.     

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.