The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved

Relationship between 18F-FDG Uptake in the Oral Cavity, Recent Dental Treatments, and Oral Inflammation or Infection: A Retrospective Study of Patients with Suspected Endocarditis

[18F]-fluorodeoxyglucose positron emission tomography ([18F]FDG PET/CT) has proven to be a useful diagnostic tool in patients with suspected infective endocarditis (IE), but is conflicting in relation to dental procedures. Questions: Is there a correlation between [18F]FDG PET/CT findings, recent dental treatment, and an affected oral cavity? (2) Is there a correlation between infective endocarditis (IE), oral health status, and (extra)cardiac findings on [18F]FDG PET/CT? Methods: This retrospective study included 52 patients. All [18F]FDG PET/CT scans were examined visually by pattern recognition using a three-point scale and semi-quantified within the volume of interest (VOI) using SUVmax. Results: 19 patients were diagnosed with IE (group 1), 14 with possible IE (group 2), and 19 without IE based on the modified Duke criteria (group 3). No correlation was found between visual PET and SUVmax and sites of oral inflammation and infection. The visual PET scores and SUVmax were not significantly different between all groups. A significant difference in the SUVmax of the valve between all groups was observed. Conclusions: This study suggests that no correlation exists between the PET findings in the oral cavity and dental treatments or inflammation/infection. No correlation between IE, actual oral health status, and extra-cardiac findings was demonstrated. Additional research is needed to conclude whether [18F]FDG PET/CT imaging is a reliable diagnostic modality for oral inflammation and infection sites

A quality, energy and environmental assessment tool for the European cold chain

According to 5th Informatory Note on Refrigeration and Food published by the International Institute of Refrigeration, 20% of the global losses in perishable products was due to lack of refrigeration. It is expected that increased use of refrigeration to reduce these losses will help meet the increasing food demands of the growing world population. However, the use of refrigeration already accounts for about 15% of world’s electricity usage. In addition, the use of refrigeration significantly contributes to global warming via emission of CO2. In this paper, a software tool was developed to assess food quality and safety evolution, energy usage and CO2 emission of different refrigeration technologies along the European cold chain. A reference product was chosen for the main different food categories in the European cold chain. Software code to predict the products temperature using the room temperature as input, based on validated heat and mass transfer models, were written in Matlab (The Mathworks Inc., Natick, USA). Also, based on validated kinetic models for the different quality indicators of the reference products, a software code was written to calculate the quality and safety evolutions of the food product, using the predicted product temperature as input. Finally, software code to calculate the energy usage and Total Equivalent Warming Impact (TEWI) value of different refrigeration technologies was also written in Matlab. All three software codes were integrated, and a graphical user interface was developed. Using the graphical user interface, a user can tailor a cold chain scenario by adding different cold chain blocks. Each cold chain block has properties that can be modified. The tool can be used to compare different cold chains with respect to quality, safety, energy usage, and environmental impact

Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

Optimal values of rovibronic energy levels for triplet electronic states of molecular deuterium

Optimal set of 1050 rovibronic energy levels for 35 triplet electronic states of $D_2$ has been obtained by means of a statistical analysis of all available wavenumbers of triplet-triplet rovibronic transitions studied in emission, absorption, laser and anticrossing spectroscopic experiments of various authors. We used a new method of the analysis (Lavrov, Ryazanov, JETP Letters, 2005), which does not need any \it a priory \rm assumptions concerning the molecular structure being based on only two fundamental principles: Rydberg-Ritz and maximum likelihood. The method provides the opportunity to obtain the RMS estimates for uncertainties of the experimental wavenumbers independent from those presented in original papers. 234 from 3822 published wavenumber values were found to be spurious, while the remaining set of the data may be divided into 20 subsets (samples) of uniformly precise data having close to normal distributions of random errors within the samples. New experimental wavenumber values of 125 questionable lines were obtained in the present work. Optimal values of the rovibronic levels were obtained from the experimental data set consisting of 3713 wavenumber values (3588 old and 125 new). The unknown shift between levels of ortho- and para- deuterium was found by least squares analysis of the $a^3\Sigma_g^+$, $v = 0$, $N = 0 \div 18$ rovibronic levels with odd and even values of $N$. All the energy levels were obtained relative to the lowest vibro-rotational level ($v = 0$, $N = 0$) of the $a^3\Sigma_g^+$ electronic state, and presented in tabular form together with the standard deviations of the empirical determination. New energy level values differ significantly from those available in literature.Comment: 46 pages, 9 picture

Phenotypic Complexity, Measurement Bias, and Poor Phenotypic Resolution Contribute to the Missing Heritability Problem in Genetic Association Studies

Background The variance explained by genetic variants as identified in (genome-wide) genetic association studies is typically small compared to family-based heritability estimates. Explanations of this ‘missing heritability’ have been mainly genetic, such as genetic heterogeneity and complex (epi-)genetic mechanisms. Methodology We used comprehensive simulation studies to show that three phenotypic measurement issues also provide viable explanations of the missing heritability: phenotypic complexity, measurement bias, and phenotypic resolution. We identify the circumstances in which the use of phenotypic sum-scores and the presence of measurement bias lower the power to detect genetic variants. In addition, we show how the differential resolution of psychometric instruments (i.e., whether the instrument includes items that resolve individual differences in the normal range or in the clinical range of a phenotype) affects the power to detect genetic variants. Conclusion We conclude that careful phenotypic data modelling can improve the genetic signal, and thus the statistical power to identify genetic variants by 20-99

Evolution of Linear Absorption and Nonlinear Optical Properties in V-Shaped Ruthenium(II)-Based Chromophores

In this article, we describe a series of complexes with electron-rich cis-{Ru^(II)(NH_3)_4}^(2+) centers coordinated to two pyridyl ligands bearing N-methyl/arylpyridinium electron-acceptor groups. These V-shaped dipolar species are new, extended members of a class of chromophores first reported by us (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 4845−4859). They have been isolated as their PF_6− salts and characterized by using various techniques including ^1H NMR and electronic absorption spectroscopies and cyclic voltammetry. Reversible Ru^(III/II) waves show that the new complexes are potentially redox-switchable chromophores. Single crystal X-ray structures have been obtained for four complex salts; three of these crystallize noncentrosymmetrically, but with the individual molecular dipoles aligned largely antiparallel. Very large molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) with an 800 nm laser and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d → π^* metal-to-ligand charge-transfer (MLCT) and π → π^* intraligand charge-transfer (ILCT) bands. The latter measurements afford total nonresonant β_0 responses as high as ca. 600 × 10^(−30) esu. These pseudo-C_(2v) chromophores show two substantial components of the β tensor, β_(zzz) and β_(zyy), although the relative significance of these varies with the physical method applied. According to HRS, β_(zzz) dominates in all cases, whereas the Stark analyses indicate that β_(zyy) is dominant in the shorter chromophores, but β_(zzz) and β_(zyy) are similar for the extended species. In contrast, finite field calculations predict that β_(zyy) is always the major component. Time-dependent density functional theory calculations predict increasing ILCT character for the nominally MLCT transitions and accompanying blue-shifts of the visible absorptions, as the ligand π-systems are extended. Such unusual behavior has also been observed with related 1D complexes (Coe, B. J. et al. J. Am. Chem. Soc. 2004, 126, 3880−3891)

Silver and Palladium Complexes of a Bis(benzimidazolin-2-ylidene)pyridine Pincer Ligand

Reaction of 2,6-bis(3-butylbenzimidazol-1-ium)pyridine dibromide with silVer oxide affords a dinuclear complex of the type [L2Ag2]2+ [L ) 2,6-bis(3-butylbenzimidazolin-2-ylidene)pyridine]. 1H NMR spectroscopic studies suggest that the dinuclear structure is also present in solution. Transmetalationof the silVer-NHC complex with PdCl2(CH3CN)2 yields a mononuclear palladium complex of the type [LPdCl]+, with a chelating C,N,C pincer ligand

Towards sustainability in cold chains: Development of a quality, energy and environmental assessment tool (QEEAT)

Quantification of the impact of refrigeration technologies in terms of the quality of refrigerated food, energy usage, and environmental impact is essential to assess cold chain sustainability. In this paper, we present a software tool QEEAT (Quality, Energy and Environmental Assessment Tool) for evaluating refrigeration technologies. As a starting point, a reference product was chosen for the different main food categories in the European cold chain. Software code to predict the products temperature, based on validated heat and mass transfer models, were written in Matlab (The Mathworks Inc., Natick, USA). Also, based on validated kinetic models for the different quality indicators of the reference products, (including fruit, meat, fish, vegetables and dairy products) a software code was written to calculate the quality and safety evolutions of the food product, using the predicted product temperature as input. Finally, software code to calculate the energy usage and Total Equivalent Warming Impact (TEWI) value of different refrigeration technologies was also written in Matlab. All three software codes were integrated, and a graphical user interface was developed. Using the QEEAT, a user can tailor a cold chain scenario by adding cold chain blocks (different steps of a cold chain) and simulating the quality evolution, energy use and emission throughout the chain. Also, the user can modify properties of a cold chain block, by selecting different technologies, or changing set point values. Defaults are provided for input values, and are based on the current practice, and obtained by extensive literature studies and consultation with different experts of the cold chain. Furthermore, the user can build and simulate several chains simultaneously, allowing him/her to compare different chains with respect to quality, energy and emission