π‐Facial Selectivity in the Formation of Tricarbonylchromium(0) Complexes of Estra‐1, 3, 5(10), 6‐tetraenes

The preparation of two η⁶‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation.     

Molecular structure and polarity of the C3NH carbene

Ab initio MP 2/4-31G ** calculations indicate that the most stable form of C₃NH is bent and singlet and that the linear structure corresponds to a maximum. The effect of changing the CNH angle on the total energy is slight, but it is quite pronounced on the molecular polarity. The wider angle tends to increase the polarity of C₃NH. MP 2/4-31G ** calculations predict a difference of polarity between linear and bent structures of 0.8 D.     

Luminescent Sensing with Quantum Dots

Summary This review highlights recent advances in the use of quantum dots (QD’s) as luminescent sensors. The bulk of the study concentrates on systems that possess organic ligands bound to the surface of QD’s. These ligands vary from low molecular weight thiols to larger molecules such as maltose binding protein. All have one thing in common: when a target analyte binds to the ligand/receptor, a perturbation of the system occurs, that registers itself as a change in the luminescence intensity of the QD. Two main mechanisms are prevalent in controlling the luminescent intensity in such systems. The first is Photoinduced Electron Transfer (PET) and the second energy transfer. This review looks at current sensors that operate by using these mechanisms. Two component systems are also investigated where a quencher is first added to a solution of the QD, followed by addition of the target analyte that interacts with the quencher to influence the luminescence intensity.     

Thermochemical studies of phthalimide and two N-alkylsubstituted phthalimides (ALKYL=ETHYL AND n-PROPYL)

The standard (p⁰=0.1 MPa) molar enthalpies of formation, Δ_fH_m⁰, for crystalline phthalimides: phthalimide, N-ethylphthalimide and N-propylphthalimide were derived from the standard molar enthalpies of combustion, in oxygen, at the temperature 298.15 K, measured by static bomb-combustion calorimetry, as, respectively, – (318.0±1.7), – (350.1±2.7) and – (377.3±2.2) kJ mol^–1. The standard molar enthalpies of sublimation, Δ_cr^gH_m⁰, at T=298.15 K were derived by the Clausius-Clapeyron equation, from the temperature dependence of the vapour pressures for phthalimide, as (106.9±1.2) kJ mol^–1 and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide as, respectively, (106.3±1.3), (91.0±1.2) and (98.2±1.4) kJ mol^–1. The derived standard molar enthalpies of formation, in the gaseous state, are analysed in terms of enthalpic increments and interpreted in terms of molecular structure.     

Composting of urban solid residues (USR) by different dispositions

The thermal behavior and non-isothermal kinetics of thermal decomposition of three different kinds of composting of the USR like: stack with drilled PVC tubes (ST), revolved stack (SR) and stack with material of structure (SM), from the usine of composing of Araraquara city, Săo Paulo state, Brazil, within a period of 132 days of composting were studied. Results from TG, DTG and DSC curves obtained on inert atmosphere indicated that the cellulosic fraction present, despite the slow degradation during the composting process, is thermally less stable than other substances originated from that process. Due to that behavior, the cellulosic fraction decomposition could be kinetically evaluated through non-isothermal methods of analysis. The values obtained were: average activation energy, Ea=248, 257 and 259 kJ mol^-1 and pre- exponential factor, logA=21.4, 22.5, 22.7 min^-1, to the ST, SR and SM, respectively. From Ea and logA values and DSC curves, Málek procedure could be applied, suggesting that the SB (Šesták-Berggren) kinetic model is the appropriated one to the first thermal decomposition step. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemometric interpretation of pesticide occurence in soil samples from an intensive horticulture area in north Portugal

An extensive monitoring programme of pesticides was carried out in soil samples from an intensive horticulture area in north of Portugal, putting into practice the needs for increased control of soil quality as far as organic pollution is concerned. The area under investigation was additionally defined as vulnerable to nitrates due to local soil and aquifer characteristics, which might be extended to pesticides contamination. Five sampling sites were selected and soils analysed at three depths in eight sampling campaigns, for the period of 2 years. A stepwise multivariate statistical approach was selected to uncover most relevant patterns inside a complex environmental data matrix. Cluster analysis was applied both to group pesticides and samples, giving a primary and unsupervised overlook of privileged relationships. Clusters of persistent pesticides and selected herbicides were identified, whereas sample classes were also formed and disposed geographically. Thirty eight percent of analysed soils samples fell into one class characterized by low contamination (class 1 in cluster analysis), which is entirely representative of the sampling site no. 1. Afterwards, linear discriminant analysis was applied to identify those pesticides, which had a higher impact in the definition of classes. Finally, factor analysis using a five component model was implemented in order to bring to light the constitution and data variance explained by each of the five main principal components, as well as, their relation to pest management practices. A factor was identified (PC1 – 22% variance) composed of chlorinated pesticides, which was representative of one of the investigated sites indicating its high contamination status. Qualitative main findings and class average concentration values were obtained through this multivariate statistical approach.     

Transuranic elements alpha-particle energy analysis using nuclear track in solids methodology

This paper presents a method for the energy analysis of alpha-particles emitted by transuranic elements via a novel technique using Nuclear Tracks. The method is based on the relationship between the energy deposited in the detection material and the diameter of the track, that is formed by chemical etching. The method involves CR-39 polycarbonate as the detector material, one-step chemical etching after irradiation, and a digital image analysis system for automatic reading of the track diameters. The experimental study included alpha-particles in the energy range 5.1 MeV to 5.8 MeV emitted by²³⁹Pu,²⁴¹Am and²⁴⁴Cm. The quantitative results provide a clear signature to identify each one of the emitters based on a characteristic track diameter.     

A short and efficient enantioselective route to a key intermediate for the total synthesis of forskolin

A simple route for the enantioselective synthesis of key intermediates (11 and 12) for the total synthesis of forskolin has been developed starting from acid 6 and (S)-alcohol 5. The latter is prepared by enantioselective catalytic CBS reduction of dienone 3, and is converted by an intramolecular Diels-Alder reaction to tricyclic lactone 9.     

A more convenient and general procedure for O-monobenzylation of diols via stannylenes: a critical reevaluation of the Bu2SnO method

A more consistent, straightforward, and economical protocol for generation of stannylene species and their reaction with BnBr leading to products of O-monobenzylation of diols has been set. It has shown to be specially indicated for substrates bearing vicinal trans 1,2-diol moieties on cyclohexane backbones, which are more resistant to these transformations. Such protocol has been successfully applied to myo-inositol derivatives and acyclic diols.     

Selective determination of copper with pyridoin phenylhydrazone as chromogenic extraction reagent

Summary The synthesis, characteristics and analytical applications of pyridoin phenylhydrazone are described. It reacts with copper(I) to produce an orange 11 complex ( _max=450 nm,=2.1×10⁴l· mole^–1·cm^–1) in aqueous ethanolic solution; it behaves as a cuproin type reagent. The orange complex can be extracted into amyl alcohol ( _max=440 nm,=2.0×10⁴l·mole^–1·cm^–1), and used for the spectrophotometric determination of trace amounts of copper. Interferences have been investigated.

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Zusammenfassung Synthese, Eigenschaften und analytische Anwendung von Pyridoin-phenylhydrazon wurden beschrieben. Es reagiert mit Cu(I) unter Bildung eines orange gefärbten 11-Komplexes in wäßrig-alkoholischer Lösung ( _max=450 nm,=2,1×10⁴l·mol^–1·cm^–1); das Reagens verhält sich ähnlich wie Cuproin. Der erwähnte Komplex läßt sich mit Amylalkohol extra-hieren ( _max=440 nm,=2,0×10⁴l·mol^–1·cm^–1) und zur spektrophoto-metrischen Bestimmung von Kupferspuren benützen. Auftretende Störungen wurden angegeben.