Three-coordinate nickel(II) and nickel(I) thiolate complexes based on the ß-diketiminate ligand system.

Mononuclear nickel(II) thiolate complexes [L(tBu)Ni(SEt)] (1) and [L(tBu)Ni(aet)] (2, aet = (-)S(CH2)2NH2) (L(tBu) = [HC(C((t)Bu)NC6H3((i)Pr)2)2](-)), supported by a bulky nacnac ligand, were synthesized by treatment of the nickel(II) bromide precursor [L(tBu)Ni(Br)] (I) with the potassium salts of ethanethiol and cysteamine, respectively. The nickel atom in 1 features a planar T-shaped environment, while the Ni ion within 2 shows a distorted square planar coordination geometry, as the aminoethanethiolate (aet) is coordinated as a chelating ligand. In 2 the ß-diketiminate ligand binds in a rarely observed κ(2)C,N coordination mode. Reduction of complex 1 or its benzenethiolate analogue [L(tBu)Ni(SPh)] (II) by KC8 resulted in the formation of dinuclear Ni(I) thiolates (K·OEt2)(K)[L(tBu)Ni(SEt)]2 (3) and (K·OEt2)2[L(tBu)Ni(SPh)]2 (4), respectively. In these compounds [L(tBu)Ni(SR)](-) units are held together by potassium cations produced in the reduction process. All compounds mentioned were structurally characterized by single-crystal X-ray crystallography.

The activation of sulfur hexafluoride at highly reduced low-coordinate nickel dinitrogen complexes.

The greenhouse gas sulfur hexafluoride is the common standard example in the literature of a very inert inorganic small molecule that is even stable against O2 in an electric discharge. However, a reduced ß-diketiminate nickel species proved to be capable of converting SF6 into sulfide and fluoride compounds at ambient standard conditions. The fluoride product complex features an unprecedented [NiF](+) unit, where the Ni atom is only three-coordinate, while the sulfide product exhibits a rare almost linear [Ni(µ-S)Ni](2+) moiety. The reaction was monitored applying (1)H NMR, IR and EPR spectroscopic techniques resulting in the identification of an intermediate nickel complex that gave insight into the mechanism of the eight-electron reduction of SF6.

The conversion of nickel-bound CO into an acetyl thioester: organometallic chemistry relevant to the acetyl coenzyme†A synthase active site.

When three become one: Within one nickel-based model system, the three reactants CO, MeI, and PhSH have been assembled to yield an acetyl thioester. The reactivity is of relevance for the functioning of the acetyl coenzyme A synthase active site and provides insights into possible binding sequences.

A combination of electroencephalogram and auditory evoked potentials separates different levels of anesthesia in volunteers.

BACKGROUND: It has been shown that the combination of electroencephalogram (EEG) and auditory evoked potentials (AEP) allows a good separation of consciousness from unconsciousness. In the present study, we sought a combined EEG/AEP indicator that allows both separation of consciousness from unconsciousness and discrimination among different levels of sedation and hypnosis over a wider range of anesthesia. METHODS: Fifteen unpremedicated volunteers received mono-anesthesia with sevoflurane or propofol in a randomized crossover design in two consecutive sessions. Loss of consciousness (LOC) and EEG burst suppression (BSP) defined end-points from the upper and lower range of general anesthesia. In addition to those two extremes, the difference between anesthetic concentration at BSP and LOC was divided into three equal intervals, resulting in two intermediate levels which divided the concentration from LOC (minimum) to BSP (maximum) into three equal steps. This data set was used to test whether a previously described combined EEG/AEP indicator "detector of consciousness" can also discriminate among degrees of anesthetic effects from the awake state to BSP. Furthermore, a new improved combined EEG/AEP indicator was developed on the basis of the data from the current study, and subsequently this new indicator was tested for its ability to separate consciousness from unconsciousness with the patient data set. RESULTS: The former "detector of consciousness" showed a prediction probability (P(K)) of 0.77 to separate different levels of anesthesia from the current study, whereas for the new combined EEG/AEP indicator, P(K) was 0.94. The new indicator was further applied to the previous study and achieved a P(K) of 0.89. CONCLUSIONS: These results show that with the new indicator presented here, a combination of EEG and AEP parameters can be used to differentiate degrees of anesthetic effects over a wide range of hypnosis, from the conscious state to deep anesthesia (i.e., BSP).

Non-targeted detection of paprika adulteration using mid-infrared spectroscopy and one-class classification - Is it data preprocessing that makes the performance?

A method for the non-targeted detection of paprika adulteration was developed using Fourier transform mid-infrared (FT-MIR) spectroscopy and one-class soft independent modelling of class analogy (OCSIMCA). One-class models based on commercially available paprika powders were developed and optimised to provide >80% sensitivity by external validation. The performances of the established models for adulteration detection were tested by predicting spiked paprika samples with various types of fraudulent material and levels of adulterations including 1% (w/w) Sudan I, 1% (w/w) Sudan IV, 3% (w/w) lead chromate, 3% (w/w) lead oxide, 5% (w/w) silicon dioxide, 10% (w/w) polyvinyl chloride, and 10% (w/w) gum arabic. Further, the influence of data preprocessing on the model performance was investigated. Relationship between classification results and data preprocessing was identified and specificity >80% was achieved for all adulterants by applying different preprocessing methods including standard normal variate (SNV), first and second derivatives, smoothing, and combinations thereof.

Nickel(I)-mediated transformations of carbon dioxide in closed synthetic cycles: reductive cleavage and coupling of CO2 generating Ni(I)CO, Ni(II)CO3 and Ni(II)C2O4Ni(II) entities.

The ß-diketiminato nickel(I) complex K2[L(tBu)Ni(I)(N2(2-))Ni(I)L(tBu)] reacts with CO2 via reductive disproportionation to form CO and CO3(2-) containing products, whereas after employment of the Ni(I) precursor [L(tBu)Ni(I)(N2)Ni(I)L(tBu)] reductive coupling of CO2 was observed giving an oxalate bridged dinickel(II) complex. The addition of KC8 to the carbonate and oxalate compounds formed leads to the regeneration of the initial Ni(I) complexes in an N2 atmosphere, thus closing synthetic cycles.

CO oxidation at nickel centres by N2O or O2 to yield a novel hexanuclear carbonate.

Reaction of a nickel(0) carbonyl complex, K(2)[L(tBu)NiCO](2), with N(2)O generates a cyclic carbonate compound composed of six [Ni(II)(CO(3))K](+) units. The same product can also be obtained using O(2) as the oxidant in a solid-state/gas reaction. These conversions represent unique examples of a nickel-bound CO oxidation by N(2)O and O(2), respectively.

Narcotrend does not adequately detect the transition between awareness and unconsciousness in surgical patients.

BACKGROUND: The Narcotrend index (MonitorTechnik, Bad Bramstedt, Germany) is a dimensionless number between 0 and 100 that is calculated from the electroencephalogram and inversely correlates with depth of hypnosis. The current study evaluates the capability of the Narcotrend to separate awareness from unconsciousness at the transition between these levels. METHODS: Electroencephalographic recordings of 40 unpremedicated patients undergoing elective surgery were analyzed. Patients were randomly assigned to receive (1) sevoflurane-remifentanil (/= 0.2 microg . kg . min), (3) propofol-remifentanil (/= 0.2 microg . kg . min). Remifentanil and sevoflurane or propofol were given until loss of consciousness. After tracheal intubation, propofol or sevoflurane was stopped until return of consciousness and then restarted to induce loss of consciousness. After surgery, drugs were discontinued. Narcotrend values at loss and return of consciousness were compared with each other, and anesthetic groups were compared. Prediction probability was calculated from values at the last command before and at loss and return of consciousness. RESULTS: At 105 of 316 analyzed time points, the Narcotrend did not calculate an index, and the closest calculated value was analyzed. No significant differences between loss and return of consciousness were found. In group 1, Narcotrend values were significantly higher than in group 3. Prediction probability was 0.501. CONCLUSIONS: In these challenging data, the Narcotrend did not differentiate between awareness and unconsciousness. In addition, Narcotrend values were not independent from the anesthetic regimen.