Ionic liquids via reaction of the zwitterionic 1,3-dimethylimidazolium-2-carboxylate with protic acids. Overcoming synthetic limitations and establishing new halide free protocols for the formation of ILs

The previously reported preparation of 1,3-dimethylimidazolium salts by the reaction of 1,3-dialkylimidazolium-2-carboxylate zwitterions with protic acids has been reinvestigated in detail, leading to the identification of two competing reactions: isomerisation and decarboxylation. The ability to control both pathways allows this methodology to be used as an effective, green, waste-free approach to readily prepare a wide range of ionic liquids in high yields. Additionally, this reaction protocol opens new possibilities in the formation of other imidazolium salts, whose syntheses were previously either very expensive (due to ion exchange protocols involving metals like Ag) or difficult to achieve (due to multiple extractions and large quantities of hard to remove inorganic by-products).

Relativistic prediction of the ground state of atomic Lawrencium

In contradiction to the prediction of the Periodic Table but in agreement with earlier suggestions by Brewer and Mann, the ground state configuration of atomic Lawrencium (Z = 103) will not be 7s^2 6d^2 D_3/2 but 7s^2 7p ^2p_1/2. The reason for this deviation from normal trends across the Periodic Table are strong relativistic effects on the outermost 7P_l/2 orbital. Multicontiguration Dirac-Fock calculations are reported for Lawrencium and analogous lighter atoms. These calculations include contributions from magnetic and retardation interactions and an estimation of quantum electrodynamic corrections.

Estimation of the ground state correlation energy for isoelectronic series of 2 to 20 electrons

Correlation energies for all isoelectronic sequences of 2 to 20 electrons and Z = 2 to 25 are obtained by taking differences between theoretical total energies of Dirac-Fock calculations and experimental total energies. These are pure relativistic correlation energies because relativistic and QED effects are already taken care of. The theoretical as well as the experimental values are analysed critically in order to get values as accurate as possible. The correlation energies obtained show an essentially consistent behaviour from Z = 2 to 17. For Z > 17 inconsistencies occur indicating errors in the experimental values which become very large for Z > 25.

Precision laser spectroscopy of the ground state hyperfine splitting of hydrogenlike ^209 Bi^82+

The first direct observation of a hyperfine splitting in the optical regime is reported. The wavelength of the M1 transition between the F = 4 and F = 5 hyperfine levels of the ground state of hydrogenlike ^209 Bi^82+ was measured to be \lamda_0 = 243.87(4) nm by detection of laser induced fluorescence at the heavy-ion storage ring ESR at GSI. In addition, the lifetime of the laser excited F = 5 sublevel was determined to be \tau_0 = 0.351(16) ms. The method can be applied to a number of other nuclei and should allow a novel test of QED corrections in the previously unexplored combination of strong magnetic and electric fields in highly charged ions.

Electronic Structure of the Ground and Low-Lying Electronic States of MoB and MoB(+)

Multiconfigurational second-order perturbation theory (CASSCF//CASPT2) and quadruple-zeta ANO-RCC basis sets were employed to investigate the ground and low-lying electronic states of MoB and MoB(+). Spectroscopic constants, potential energy curves, wavefunctions, Mulliken population analyses, and ionization energies are given. The ground state of MoB is of X(6)Pi symmetry (R(e) = 1.968 angstrom, omega(e) = 664 cm(-1), and mu = 2.7 D), giving rise to a Omega = 7/2 ground state after including spin-orbit coupling. For MoB(+), the ground state is computed to be of X(7)Sigma(+) symmetry (R(e) = 2.224 angstrom, omega(e) = 141 cm(-1), and mu = 1.2 D), with an adiabatic ionization energy of 7.19 eV and a vertical one of 7.53 eV. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3362-3370, 2011

Reaction of the lateral periodontium of dogs' teeth to contaminated and noncontaminated perforations filled with mineral trioxide aggregate

It has been shown that the mineral trioxide aggregate (MTA) used to seal lateral/furcal perforations stimulates the deposition of newly formed cementum. Nevertheless, when the site of the perforation is contaminated, the healing process might occur under less favorable conditions. This study evaluated the repair healing process of noncontaminated and contaminated lateral perforations filled with MTA and the effect of previously filling the contaminated perforations with a bactericidal agent. Thirty lateral root perforations were prepared in endodontically treated dog's teeth, thus forming 3 groups with 10 specimens each. In group 1 the perforations were immediately sealed with MTA. In group 2 the perforations were left open for 7 days and thereafter sealed with MTA. In group 3 the perforations were left open for 7 days, filled temporarily with a calcium hydroxide-based paste for 14 days, and then sealed with MTA. The animals were killed after 90 days, and the pieces were prepared for histomorphologic and histomicrobiologic evaluations. The statistical analysis showed that group 1 had significantly better repair than groups 2 (P <.05) and 3 (P <.05), which validates the superior results obtained when MTA was immediately used to seal root perforations. Groups 2 and 3 had statistically similar repair to each other (P >.05). There were a larger number of cases of complete or partial biologic seal in group 1 compared with the contaminated groups. It might be concluded that the lateral root perforations sealed with MTA after contamination presented worse repair than the noncontaminated, immediately sealed perforations. The temporary filling with a bactericidal agent (calcium hydroxide-based paste) did not improve the repair of perforations exposed to contamination, and the contaminated groups presented similar results to each other.

Tissue reaction of the EndoREZ in root canal fillings short of or beyond an apical foramenlike communication

This study evaluated the response of periapical tissues to the endodontic sealer EndoREZ in root canal fillings short of or beyond the apical foramenlike communication. Twenty root canals of premolars and incisors of 2 mongrel dogs were used. After coronal access and pulp extirpation, the canals were instrumented up to a size 55 K-file and the apical cemental barrier was penetrated with a size 15 K-file to create an apical foramenlike communication, which was widened to a size 25 K-file. The canals were irrigated with saline at each change of file. The root canals were obturated either short of or beyond the apical foramenlike opening by the lateral condensation of gutta-percha and EndoREZ, originating 2 experimental groups: G1, EndoREZ/short of the apical foramenlike opening, and G2, EndoREZ/beyond the apical foramenlike opening. The animals were killed by anesthetic overdose 90 days after endodontic treatment. The individual roots were obtained and serial histological sections were prepared for histomorphological analysis (H&E and Brown and Brenn techniques) under light microscopy. The following parameters were examined: closure of the apical foramenlike communication and apical opening of accessory canals, apical cementum resorptions, intensity of the inflammatory infiltrate, presence of giant cells, and thickness and organization of the apical periodontal ligament. Each parameter was scored 1 to 4, 1 being the best result and 4 the worst. Data were analyzed statistically by the Wilcoxon nonparametric tests (P = .05). Comparing the 2 groups, the best result (P = .05) was obtained with root canal filling with EndoREZ short of the apical foramenlike opening. In conclusion, limiting the filling material to the root canal space apically was important to determine the best treatment outcome when EndoREZ was used as the sealer. (Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2010; 109: e94-e99)

Cycloaddition reaction of the azido-bridged cyclometallated complex [Pd(dmba)N-3](2) with CS2. Crystal and molecular structure of DI(mu, N,S-1,2,3,4-thiatriazole-5-thiolate) bis[(N,N-dimethylbenzyl-amine-C-2,N)palladium(II)]

The 1,3-dipolar cycloaddition of carbon disulfide to the coordinated azide in the cyclometallated compound [Pd(dmba)(N-3)](2) (1), dmba = N,N-dimethylbenzylamine, was investigated. The compound obtained di(mu, N,S-1,2,3,4-thiatriazole-5-thiolate)-bis[(N,N-dimethylbenzylamine-C-2,N)palladium(II)] (2), was characterized by IR spectroscopy and X-ray diffraction. Complex (2) is dimeric with the two [Pd(N,N-dimethylbenzylamine)] moieties being connected by the two vicinal bridging N,S-1,2,3,4-thiatriazole-5-thiolate anions in a square-planar coordination for the palladium atoms.

Evaluation of the components of production of the ricinus according of rates of calcareous rock and match

The soil of the Paraiba, in generality, are acid and with low levels of available match, seriously limiting the income of the plants. A research in vegetation house was lead, with the objective to evaluate doses of calcareous soil and match in the culture of ricinus. The treatments had been composites for five levels of match: 0.0; 80; 160; 240 and 360 kg ha(-1) of P(2)O(5) and four dosis of calcareous rock: 0.0; 2.5; 3.5 and 4.5 t ha(-1) in experimental delineation of blocks casualized with 4 factorial project x 3 (four levels of match and three doses of calcareous soil) more two treatments you add zero of match (0.0 P(2)O(5): 2,5 t ha(-1) of calcareous soil) and calcareous soil zero (240 P(2)O(5): 0.0 t ha(-1) of calcareous soil), with three repetitions. The calcareous soil reduced the acidity of the ground and effect of the application of the match (>= 80 kg ha(-1) of P(2)O(5)) in the presence of the collagen (>= 2.5 t ha(-1) of CaCO(3)) with of the calcareous soil (>= 2.5 t ha(-1) of CaCO(3)) in the presence of the match was not verified well (>= 80 kg ha(-1) of P(2)O(5)). The match applied in the absence of the calcareous soil was limited to the income of the culture of what the calcareous soil in the absence of the match.

Reaction of the human gingival tissue to different suture materials used in periodontal surgery.

The gingival reaction to 4 different suture materials used in periodontal surgery was studied in 36 patients. The gingiva was sutured prior to surgery and biopsies were taken at 3, 7 and 14 days to observe the tissue reaction. The histological examination showed that silk caused the most intense and longest inflammatory response. Polyester and perlon provoked shorter, less intense tissue reactions than silk, and nylon caused the least inflammatory response, with earlier tissue repair.

Rarefied allelic richness of the ground beetle Abax parallelepipedus in Germany

Although genetic diversity is one of the key components of biodiversity, its drivers are still not fully understood. While it is known that genetic diversity is affected both by environmental parameters as well as habitat history, these factors are not often tested together. Therefore, we analyzed 14 microsatellite loci in Abax parallelepipedus, a flightless, forest dwelling ground beetle, from 88 plots in two study regions in Germany. We modeled the effects of historical and environmental variables on allelic richness, and found for one of the regions, the Schorfheide-Chorin, a significant effect of the depth of the litter layer, which is a main component of habitat quality, and of the sampling effort, which serves as an inverse proxy for local population size. For the other region, the Schwäbische Alb, none of the potential drivers showed a significant effect on allelic richness. We conclude that the genetic diversity in our study species is being driven by current local population sizes via environmental variables and not by historical processes in the studied regions. This is also supported by lack of genetic differentiation between local populations sampled from ancient and from recent woodlands. We suggest that the potential effects of former fragmentation and recolonization processes have been mitigated by the large and stable local populations of Abax parallelepipedus in combination with the proximity of the ancient and recent woodlands in the studied landscapes.

Determination of Dipyrone in pharmaceutical preparations based on the chemiluminescent reaction of the quinolinic hydrazide-H2O2-vanadium (IV) system and flow injection analysis

A rapid, economic and sensitive chemiluminescent method involving flow-injection analysis was developed for the determination of dipyrone in pharmaceutical preparations. The method is based on the chemiluminescent reaction between quinolinic hydrazide and hydrogen peroxide in a strongly alkaline medium, in which vanadium(IV) acts as a catalyst. Principal chemical and physical variables involved in the flow-injection system were optimized using a modified simplex method. The variations in the quantum yield observed when dipyrone was present in the reaction medium were used to determine the concentration of this compound. The proposed method requires no preconcentration steps and reliably quantifies dipyrone over the linear range 1–50 µg/mL. In addition, a sample throughput of 85 samples/h is possible. Copyright © 2011 John Wiley & Sons, Ltd.

Reaction of the Escherichia coli quinol oxidase cytochrome bo3 with dioxygen: the role of a bound ubiquinone molecule.

We have studied the kinetics of the oxygen reaction of the fully reduced quinol oxidase, cytochrome bo3, using flow-flash and stopped flow techniques. This enzyme belongs to the heme-copper oxidase family but lacks the CuA center of the cytochrome c oxidases. Depending on the isolation procedure, the kinetics are found to be either nearly monophasic and very different from those of cytochrome c oxidase or multiphasic and quite similar to cytochrome c oxidase. The multiphasic kinetics in cytochrome c oxidase can largely be attributed to the presence Of CuA as the donor of a fourth electron, which rereduces the originally oxidized low-spin heme and completes the reduction of O2 to water. Monophasic kinetics would thus be expected, a priori, for cytochrome bo3 since it lacks the CuA center, and in this case we show that the oxygen reaction is incomplete and ends with the ferryl intermediate. Multiphasic kinetics thus suggest the presence of an extra electron donor (analogous to CuA). We observe such kinetics exclusively with cytochrome bo3 that contains a single equivalent of bound ubiquinone-8, whereas we find no bound ubiquinone in an enzyme exhibiting monophasic kinetics. Reconstitution with ubiquinone-8 converts the reaction kinetics from monophasic to multiphasic. We conclude that a single bound ubiquinone molecule in cytochrome bo3 is capable of fast rereduction of heme b and that the reaction with O2 is quite similar in quinol and cytochrome c oxidases.