The use of multivariate modelling of near infra-red spectra to predict the butter fat content of spreads

In order to obtain a rapid method that can detect adulteration of butter fats with cheaper vegetable fats, the use of NIR spectroscopy and multivariate modelling was explored. For model building and validation, an extensive set of samples was collected, consisting of 152 butter samples, 42 oils and 200 blends thereof. Variations in butter fat composition are reflected in distinct NIR spectral regions. Principal components analysis and partial least square discriminant analysis was used to inspect the variation within the sample set. As reference values for training partial least squares models, butter fat levels as declared by suppliers were taken, as well as C4:0 fatty acid levels as measured directly by GC. All samples were used for training, except for 100 blends, which were used later for validation. Different pre-processing and PLS approaches were explored, resulting in models that had a RMSEPs for butter fat and C4:0 fatty acid level in the range of 4.3-8.2 and 0.33-0.38% (w/w), respectively. The performance of NIR in assessment of C4:0 fatty acid levels is lower as for GC, but this disadvantage is outweighed by shorter measurement times and the lower skill levels required. Furthermore NIR is able to assess overall levels of butter fat, in addition to the indirect indicator provided by the C4:0 fatty acid level.     

Slice imaging of the quantum state-to-state cross section for photodissociation of state-selected rovibrational bending states of OCS (v2=0,1,2/JlM)+hnu-->CO(J)+S(1D2)

Using hexapole quantum state-selection of OCS (v(2)=0,1,2/JlM) and high-resolution slice imaging of quantum state-selected CO(J), the state-to-state cross section OCS (v(2)=0,1,2/JlM)+hnu-->CO(J)+S((1)D(2)) was measured for bending states up to v(2)=2. The population density of the state-selected OCS (v(2)=0,1,2 /JlM) in the molecular beam was obtained by resonantly enhanced multiphoton ionization of OCS and comparison with room temperature bulk gas. A strong increase of the cross section with increasing bending state is observed for CO(J) in the high J region, J=60-67. Integrating over all J states the authors find sigma(v(2)=0):sigma(v(2)=1):sigma(v(2)=2)=1.0:7.0:15.0. A quantitative comparison is made with the dependence of the transition dipole moment function on the bending angle.     

Donor-functionalized polydentate pyrylium salts and phosphinines: synthesis, structural characterization, and photophysical properties

A series of donor-functionalized pyrylium salts have been prepared by classical condensation reactions which were further converted into the corresponding thienyl- and pyridyl-substituted polydentate lambda(3)-phosphinines by reaction with P(SiMe(3))(3). Further chemical modification of these phosphorus heterocycles with Hg(OAc)(2) in the presence of methanol resulted in the formation of lambda(5)-phosphinines. The photophysical properties of a selected series of thienyl- and pyridyl-functionalized pyrylium salts, lambda(3)- and lambda(5)-phosphinines, were investigated and the results compared and supported by theoretical calculations on the DFT level. Significant fluorescence was observed for the pyrylium salts and lambda(5)-phosphinines. In contrast, the heteroaromatic substituted lambda(3)-phosphinines show very little emission which is consistent with the low oscillator strength predicted by DFT calculations for this pi-->pi* transition. Furthermore, all three classes of compounds show readily observable phosphorescence in solution, which was determined by time-gated detection at low temperature.     

PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Development and validation of an analytical method for detection of estrogens in water

An analytical procedure enabling routine analysis of four environmental estrogens at concentrations below 1 ng L^–1 in estuarine water samples has been developed and validated. The method includes extraction of water samples using solid-phase extraction discs and detection by gas chromatography (GC) with tandem mass spectrometry (MS–MS) in electron-impact (EI) mode. The targeted estrogens included 17- and 17-estradiol (aE2, bE2), estrone (E1), and 17-ethinylestradiol (EE2), all known environmental endocrine disruptors. Method performance characteristics, for example trueness, recovery, calibration, precision, accuracy, limit of quantification (LOQ), and the stability of the compounds are presented for each of the selected estrogens. Application of the procedure to water samples from the Scheldt estuary (Belgium – The Netherlands), a polluted estuary with reported incidences of environmental endocrine disruption, revealed that E1 was detected most frequently at concentrations up to 7 ng L^–1. aE2 was detected once only and concentrations of bE2 and EE2 were below the LOQ.Presented at the 9th FECS Conference on Chemistry and the Environment, Bordeaux, France, 29 August–1 September 2004     

Synthesis and spectroscopic characterization of a new family of Ni(4) spin clusters

A new family of tetranuclear Ni complexes [Ni(4)(ROH)(4)L(4)] (H(2)L = salicylidene-2-ethanolamine; R = Me (1) or Et (2)) has been synthesized and studied. Complexes 1 and 2 possess a [Ni(4)O(4)] core comprising a distorted cubane arrangement. Magnetic susceptibility and inelastic neutron scattering studies indicate a combination of ferromagnetic and antiferromagnetic pairwise exchange interactions between the four Ni(II) centers, resulting in an S = 4 spin ground state. Magnetization measurements reveal an easy-axis-type magnetic anisotropy with D approximately -0.93 cm(-)(1) for both complexes. Despite the large magnetic anisotropy, no slow relaxation of the magnetization is observed down to 40 mK. To determine the origin of the low-temperature magnetic behavior, the magnetic anisotropy of complex 1 was probed in detail using inelastic neutron scattering and frequency domain magnetic resonance spectroscopy. The spectroscopic studies confirm the easy-axis-type anisotropy and indicate strong transverse interactions. These lead to rapid quantum tunneling of the magnetization, explaining the unexpected absence of slow magnetization relaxation for complex 1.     

The determination of ammonia in flue gas from the selective catalytic reduction of nitric oxide with ammonia

The emission of NO_x from coal-fired boilers can be limited by means of the selective catalytic reduction of NO_x with ammonia. The amounts of unreacted ammonia downstream should be low to avoid processing and environmental problems. Continuous measurement of the ammonia in the flue gas is needed. The determination of ammonia and flue gas sampling techniques are discussed. Measurements of ammonia in exhausts of a laboratory reactor and of a pilot plant for the selective catalytic reduction of NO_x with ammonia are presented. Ammonia was determined by mass spectrometry and chemiluminescence in the gas phase, and by spectrophotometric (Nessler and Berthollet reactions) or potentiometry in aqueous solution, in low (<5 μl l^?1) and high (<1000 μl l^?1) concentration ranges.     

Kalman filter applied to setpoint control in continuous titrations

A state-space model is described for continuous titrations based on first-order dynamics. The Kalman filter allows on-line monitoring of an empirically established setpoint in the titration curve. The algorithm advocated is examined for potentiometric titrations of ca. 10^?3 M solutins of acids, silver(I) and copper(II). Only gross indications of the essential parameters such as the time constant and noise covariances are required. The computer-controlled titration system is compared with a conventional setpoint titrator. Especially in cases of slow response times and steep inflections, there are advantages in both accuracy and speed when the Kalman filter is applied.     

Syntheses of dibenzo[b,e][1,4]dioxin derivatives via iron complexes, and further functionalizations via directed metallation

Double nucleophilic aromatic substitution reactions between (cyclopentadienyl)(η⁶-1,2-dichlorobenzene)iron(1 + ) salts and substituted 1,2benzenediols have been carried out under mild conditions to prepare [η⁶-dibenzo[b,e][1,4]dioxin]iron(1 + ) complexes functionalized in the 1- or 2-position with an alkyl, aldehyde, carboxylic acid, methoxycarbonyl, carboxamide, or hydroxy group. 3-Methyl- and 4-methyl-(η⁶-1,2-dichlorobenzene)iron complexes were treated with substituted 1,2-benzenediols to effect functionalization of both aromatic rings of the heterocycle. The dibenzodioxin ligands were liberated routinely by irradiation with ultraviolet light. Directed deprotonation of the free functionalized dibenzodioxins with an alkyllithium reagent followed by quenching with a variety of electrophiles yielded further derivatives, including two new isoindolone systems.