Is allylphosphine a carbon or a phosphorus base in the gas phase?

The gas-phase basicity of allylphosphine (2-propenylphosphine) was measured by means of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry techniques. A complete survey of the allylphosphine-H(+) potential energy surface, carried out through the use of high-level G2(MP2) and B3LYP/6-311+G(3df,2p) calculations, allows us to conclude that, under low-pressure, low-energy ICR conditions, the interaction between the protonated reference base, B(ref)H(+), and allylphosphine leads to a complex in which B(ref)H(+) attaches to the phosphorus atom of allylphosphine, where the electrostatic potential is strongly attractive. Hence, in the first step only the phosphorus protonated species should be formed. Its isomerization to yield the C(beta)-protonated form, which is the global minimum of the potential energy surface, implies a very high activation barrier that cannot be overtaken under normal experimental ICR conditions. Therefore, the main conclusion of our study is that allylphosphine behaves as a phosphorus base in the gas phase, even though the C(beta)-protonated structure is the most stable protonated species. We have also shown that both C(beta)- and C(gamma)-protonation triggers a cyclization of the system. An analysis of the bonding of the different protonated species as compared with that of the neutral system is presented.     

Antibacterial and Photocatalytic Properties of ZnO Nanoparticles Obtained from Chemical versus Saponaria officinalis Extract-Mediated Synthesis

In the present work, the properties of ZnO nanoparticles obtained using an eco-friendly synthesis (biomediated methods in microwave irradiation) were studied. Saponaria officinalis extracts were used as both reducing and capping agents in the green nanochemistry synthesis of ZnO. Inorganic zinc oxide nanopowders were successfully prepared by a modified hydrothermal method and plant extract-mediated method. The influence of microwave irradiation was studied in both cases. The size, composition, crystallinity and morphology of inorganic nanoparticles (NPs) were investigated using dynamic light scattering (DLS), powder X-ray diffraction (XRD), SEM-EDX microscopy. Tunings of the nanochemistry reaction conditions (Zn precursor, structuring agent), ZnO NPs with various shapes were obtained, from quasi-spherical to flower-like. The optical properties and photocatalytic activity (degradation of methylene blue as model compound) were also investigated. ZnO nanopowders’ antibacterial activity was tested against Gram-positive and Gram-negative bacterial strains to evidence the influence of the vegetal extract-mediated synthesis on the biological activity.     

Ga+ Basicity and Affinity Scales Based on High‐Level Ab Initio Calculations

The structure, relative stability and bonding of complexes formed by the interaction between Ga⁺ and a large set of compounds, including hydrocarbons, aromatic systems, and oxygen‐, nitrogen‐, fluorine and sulfur‐containing Lewis bases have been investigated through the use of the high‐level composite ab initio Gaussian‐4 theory. This allowed us to establish rather accurate Ga⁺ cation affinity (GaCA) and Ga⁺ cation basicity (GaCB) scales. The bonding analysis of the complexes under scrutiny shows that, even though one of the main ingredients of the Ga⁺‐base interaction is electrostatic, it exhibits a non‐negligible covalent character triggered by the presence of the low‐lying empty 4p orbital of Ga⁺, which favors a charge donation from occupied orbitals of the base to the metal ion. This partial covalent character, also observed in AlCA scales, is behind the dissimilarities observed when GaCA are compared with Li⁺ cation affinities, where these covalent contributions are practically nonexistent. Quite unexpectedly, there are some dissimilarities between several Ga⁺‐complexes and the corresponding Al⁺‐analogues, mainly affecting the relative stability of π‐complexes involving aromatic compounds.     

Ultrastructure of the skin melanophores and iridophores in paddlefish, Polyodon spathula

The ultrastructure of melanophores and iridophores of Polyodon spathula has been examined by transmission electron microscopy. In the skin, two types of chromatophores, melanophores and iridophores were founded. Melanophores were localized both in epidermis and dermis. Epidermal melanophores were present on the dorsal region of the trunk, sides, outer surface of the operculum and rostrum. Iridophores were founded in the dermis from ventral skin. The cytoplasm of iridophores is filled with reflecting platelets with variable orientation. The length of the long axis of the platelets varies from 1 to 2.10 microm.     

High-level ab initio versus DFT calculations on (H2O2)2 and H2O2–H2O complexes as prototypes of multiple hydrogen bond systems

The performance of B-LYP, B-P86, B3-LYP, B3-P86, and B3-PW91 density functionals to describe multiple hydrogen bond systems was studied. For this purpose we have chosen the dimers of hydrogen peroxide and the hydrogen peroxide–water complexes. The geometries and vibrational frequencies obtained with a 6-311+G(d,p) basis set were compared with those obtained at the MP2 level using the same basis set expansion. The corresponding dimerization energies were obtained using a 6-311+G(3df,2p) basis set and compared with those obtained using the G2(MP2) theory. Red shiftings of the OH donor stretching frequencies were predicted by all approaches investigated; however, in all cases, the DFT values were sizably larger than the MP2 ones. Similarly, the blue shifting of the torsion of the hydrogen peroxide subunit was larger when evaluated at the DFT level. All functionals reproduced the G2(MP2) relative stabilities of the different local minima quite well. With the exception of the B-LYP and B3-PW91 approaches, all functionals yielded binding energies which deviated from the G2(MP2) values by less than 0.5 kcal/mol, provided that G2-type basis sets were used and that the corresponding BSSE corrections were included. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1124–1135     

Encapsulation of manganese(III) complex in NaY nanoporosity for heterogeneous catalysis

An encapsulated Mn(III)–salen complex in NaY was synthesized and characterized, and the catalytic behaviour of the complex was evaluated by the oxidation of styrene. The encapsulation was achieved by two different methodologies designated as the flexible ligand method (A) and the method of in situ complex synthesis (B). The characterizations of the free complex as well as the catalysts with and without the complex were performed by powder X‐ray diffraction, scanning electron microscopy, chemical analysis and FT‐IR spectroscopy. Both prepared catalysts are active in the oxidation of styrene in the presence of tert‐butyl hydroperoxide (tBuOOH) and lead to styrene epoxide and benzaldehyde. The localization of the complex in zeolite plays an important role in the catalytic activity of these heterogeneous catalysts. Copyright © 2011 John Wiley & Sons, Ltd.     

Microsolvation of morpholine,a bidentate base – the importance of cooperativity

The structure, relative energies, and bonding in morpholine(water)_n (n = 1–4) clusters have been investigated at the Becke, three‐parameter, Lee–Yang–Parr/6–311 + G(3df,2p)//Becke, three‐parameter, Lee–Yang–Parr/6–311 + G(d,p) level of theory. Cooperative effects have been analyzed through the use of structural, energetic, and electron density indexes. Our analysis shows that these effects are crucial to trace the relative stability of the complexes formed. In all cases water molecules prefer to self‐associate forming chains in which each individual molecule behaves as a hydrogen bond (HB) donor and HB acceptor. The chain so formed behaves in turn as HB donor and HB acceptor with respect to morpholine, being the most stable arrangements those in which the NH group of morpholine behaves simultaneously as HB donor and HB acceptor. Higher in energy lie complexes in which the HB acceptor continues to be the NH group, but the HB donor is a CH group, or alternative structures in which the HB acceptor is the ether‐like oxygen of morpholine and the HB donor its NH group. Cooperativity increases with the number of solvent molecules, but there is a clear attenuation effect. Thus, whereas the additive interaction energy on going from dihydrated to trihydrated species increases by a factor of 3, this increase is about half on going from trihydrated to tetrahydrated complexes. Copyright © 2012 John Wiley & Sons, Ltd.     

European ring exercise on water toxicity using different bioluminescence inhibition tests based on Vibrio fischeri, in support to the implementation of the water framework directive

An inter-laboratory comparison exercise was conducted under the European Union funded project entitled: Screening Methods for Water Data Information in Support of the Implementation of the Water Framework Directive (SWIFT-WFD) and coordinated by the Consejo Superior de Investigaciones Científicas (CSIC), in order to evaluate the reproducibility of different toxicity tests based on the bioluminescence inhibition of Vibrio fischeri, for the rapid water toxicity assessment.For the first time, this type of exercise has been organized in Europe, and using different tests based on the same principle. In this exercise, 10 laboratories from 8 countries (Austria, Cyprus, Germany, Greece, Italy, Portugal, Romania, and Spain) took place, and a total number of 360 samples were distributed.During the exercise, six series of six samples were analyzed along 5 months. Every batch of samples was composed by three real samples and three standard solutions. The real samples were: a raw influent and the effluent of a wastewater treatment plant (WWTP), and a sample from a first settlement of the WWTP spiked with a mixture of toxicant standards.A final number of 330 (91.7%) samples was analyzed, 3300 values in duplicate were collected, and the results for each sample were expressed as the 50% effective concentration (EC₅₀) values calculated through five points of dilution inhibition curves, after 5 and 15 min of incubation times.A statistical study was initiated using 660 results. The mean values, standard deviations (σ), variances (σ²), and upper and lower warning limits (UWL and LWL) were obtained, using the EC₅₀ values calculated with the result from the participating laboratories.The main objectives of this toxicity ring study were to evaluate the repeatability (r) and reproducibility (R) when different laboratories conduct the test, the influence of complex matrix samples, the variability between different tests based on the same principle, and to determine the rate at which participating laboratories successfully completed tests initiated.In this exercise, the 3.93% toxicity values were outliers according with the Z-score values and the Dixon test. The samples with the greater number of outliers were those with the smallest variability coefficient, corresponding to the greater and the smaller toxicity level.No relation was found through the cluster analysis, between the final results and the different commercial devices involved. Testing by multiple commercial devices did not appear to reduce the precision of the results, and the variability coefficient for the exercise was nearby to the average value for past editions carried out at national level, where the different participants used the same commercial device.Stability of samples was also followed during the exercise. While statistical significance differences were not found for the greater part of samples, for the sample from the WWTP influent, a significant decrease of the toxicity value was found along this study. Nevertheless, this was a type of sample with a high toxicity level during all the exercise.On the other hand, in order to obtain the chemical characterization of real samples, those were analyzed by chromatographic techniques, using different sequential solid phase extraction (SSPE) procedures, followed by liquid chromatography coupled with mass spectrometry (LC-MS), and gas chromatography-mass spectrometry (GC-MS). Good agreement was found between the chemical analysis results and the toxicity level of the samples.     

Substituent effects on enthalpies of formation of nitrogen heterocycles: 2-substituted benzimidazoles and related compounds

The enthalpies of combustion, heat capacities, enthalpies of sublimation and enthalpies of formation of 2-tert-butylbenzimidazole (2tBuBIM) and 2-phenylimidazole (2PhIM) are reported and the results compared with those of benzene derivatives and a series of azoles (imidazoles, pyrazoles, benzimidazoles and indazoles). Theoretical estimates of the enthalpies of formation were obtained through the use of atom equivalent schemes. The necessary energies were obtained in single-point calculations at the B3LYP/6-311++G(d,p) on B3LYP/6-31G optimized geometries. The comparison of experimental and calculated values of all studied compounds bearing H (unsubstituted), methyl (Me) ethyl (Et), propyl (Pr), isopropyl (iPr), tert-butyl (tBu), benzyl (Bn) and phenyl (Ph) groups show remarkable homogeneity. The remarkable consistency of both the calculated and experimental results allows us to predict with reasonable certainty the missing experimental values. The crystal and molecular structure of the 2-benzylbenzimidazole (2BnBIM) has been determined by X-ray analysis. The observed molecular conformation permits the crystal being built up through N-H...N hydrogen bonds and van der Waals contacts between the molecules. An attempt has been made to relate the crystal structure to the enthalpies of sublimation.