A stable carbonyl-pyrazine-metal(0) complex: Synthesis and characterization of cis-tetracarbonylpyrazinetrimethylphosphitetungsten(0)

Pentacarbonylpyrazinetungsten(0), (CO)₅W(pyz), is not stable in solution in polar solvents such as acetone or dichloromethane and undergoes conversion to a bimetallic complex, (CO)₅W(pyz)W(CO)₅ plus free pyrazine. These three species exist at equilibrium. Using the quantitative ¹H NMR spectroscopy, the equilibrium constant could be determined to be K_eq = (5.9 ± 0.8) × 10⁻² at 25 °C. Introducing a second pyrazine ligand into the molecule does not stabilize the complex, as cis-W(CO)₄(pyz)₂ was found to be less stable than W(CO)₅(pyz) and, therefore, could not be isolated. However, introducing trimethylphosphite as a donor ligand into the complex leads to the stabilization of the carbonyl-pyrazine-metal(0) complexes, as shown by the synthesis of cis-W(CO)₄[P(OCH₃)₃](pyz). This complex could be isolated from the reaction of the photogenerated W(CO)₄[P(OCH₃)₃](tetrahydrofuran) with trimethylphosphite upon mixing for 2 h at 10 °C in tetrahydrofuran and characterized by elemental analysis, IR, MS, ¹H, ¹³C, and ³¹P NMR spectroscopy.     

Veronicosid,ein neues Iridoidglucosid aus Veronica officinalisL.(Scrophulariaceae)

Veronicoside, a new iridoid glucoside from Veronica officinalis L. (Scrophulariaceae) A new iridoid glucoside, Veronicoside ( 1 ) has been isolated from Veronica officinalis L. The structure of 1 has been determined by chromatographic and spectroscopic analysis as 6-benzoylcatalpol.     

Interactions of gamma rays with undoped and Mn-doped sodium phosphate glasses

Ultraviolet and visible spectroscopic measurements were used to investigate prepared undoped and Mn-doped sodium phosphate glasses before and after successive gamma irradiation. The effects of both glass composition and MnO₂ content on the generation of radiation-induced defects were investigated. Undoped sodium phosphate glass shows strong UV absorption, which is attributed to the presence of trace iron impurities present in the raw materials. Mn-doped glasses reveal an additional visible broad band centered at about 500 nm due to Mn³⁺, which has recently been related to the ⁵E_g →⁵T_2g transition. The radiation-induced bands are correlated with the generation of liberated electron–hole pairs during the process of gamma irradiation and the possibility of photochemical reactions especially with trace iron impurities and manganese ions. The intensity and the position of the induced bands are observed to depend on the type and composition of glass, concentration of the dopant and also on the irradiation dose. Manganese ions when present in relatively higher content have been found to show a shielding behavior towards the effects of progressive gamma irradiation causing a retardation of the growth of the induced defects. Infrared and Raman spectra of the undoped and Mn-doped glasses were measured to investigate the structural phosphate groups present and the effect of MnO₂ on the network structure. An ESR investigation was carried out to confirm the state of manganese ions in the prepared sodium phosphate glasses.     

Sur quelques Théorémes globaux en geometrie finslérienne

Résumè Le travail suivant établit des théorèmes globaux relatifs aux variétes finslériennes completes dont le tenseur de courbure vérifie certaines hypothèses. Le théorème de Hopf-Rinow est d’abord démontrè, puis au moyen du calcul variationnel, on établit une géneralisation des théoremes de Myers, de Cartan et de L. W. Green.     

Three‐dimensional visible‐light capsule enclosing perfect supersized darkness via antiresolution

Supersized darkness in three dimensions surrounded by all light in free space is demonstrated theoretically and experimentally in the visible regime. The object staying in the darkness is similar to staying in an empty light capsule because light just bypasses it by resorting to destructive interference. A binary‐optical system is designed and fabricated based on achieving antiresolution (AR), by which electromagnetic energy flux avoids and bends smoothly around a nearly perfect darkness region. AR remains an unexplored topic hitherto, in contrast to the super‐resolution for realizing high spatial resolution. This novel scheme replies on smearing out the point spread function and thus poses less stringent limitations upon the object's size and position since the created dark (zero‐field) area reach 8 orders of magnitude larger than λ² in cross‐sectional size. It functions very well with arbitrarily polarized beams in three dimensions, which is also frequency scalable in the whole electromagnetic spectrum.     

Nanocrystallization of an amorphous Fe<Subscript>80</Subscript>B<Subscript>20</Subscript> alloy during severe plastic deformation

The structural evolution of an amorphous Fe₈₀B₂₀ alloy subjected to severe plastic deformation at room temperature or at 200°C was studied. Deformation leads to the formation of α-Fe nanocrystals in an amorphous phase. After room-temperature deformation, nanocrystals are localized in shear bands. After deformation at 200°C, the nanocrystal distribution over the alloy is more uniform. Possible causes of the crystallization of the amorphous phase during severe plastic deformation are discussed.     

Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction

In this paper we report the effect of dicationic ‘gemini’ surfactants (CH₃)₂C₁₆H₃₃N⁺? (CH₂)_m? N⁺C₁₆H₃₃(CH₃)₂, 2Br^? (where m = 4, 5, 6) on the reaction of ninhydrin with DL ‐tryptophan. The gemini surfactant micellar media are comparatively more effective than their conventional monomeric counterpart cetyltrimethylammonium bromide (CTAB) micelles. Also, whereas typical rate constant (k_ψ) increase and leveling‐off regions, just like CTAB, are observed with geminis, the latter produce a third region of increasing k_ψ at higher concentrations. These subsequent increases are ascribed to changes in micellar morphologies, consistent with changes in ¹H NMR line widths. Quantitative kinetic analysis of the rate constant–[surfactant] data has been performed on the basis of modified pseudophase model. Copyright © 2007 John Wiley & Sons, Ltd.     

A nonnormal look at polychoric correlations: modeling the change in correlations before and after discretization

Two algorithms for establishing a connection between correlations before and after ordinalization under a wide spectrum of nonnormal underlying bivariate distributions are developed by extending the iteratively found normal-based results via the power polynomials. These algorithms are designed to compute the polychoric correlation when the ordinal correlation is specified, and vice versa, along with the distributional properties of latent, continuous variables that are subsequently ordinalized through thresholds dictated by the marginal proportions. The method has broad applicability in the simulation and random number generation world where modeling the relationships between these correlation types is of interest.     

Impact of Multi-Component Surrogates on the Performances,Pollutants, and Exergy of IC Engines

Even though there is a pressing interest in clean energy sources, compression ignition (CI) engines, also called diesel engines, will remain of great importance for transportation sectors as well as for power generation in stationary applications in the foreseeable future. In order to promote applications dealing with complex diesel alternative fuels by facilitating their integration in numerical simulation, this paper targets three objectives. First, generate novel diesel fuel surrogates with more than one component. Here, five surrogates are generated using an advanced chemistry solver and are compared against three mechanisms from the literature. Second, validate the suggested reaction mechanisms (RMs) with experimental data. For this purpose, an engine configuration, which features a reacting spray flow evolving in a direct-injection (DI), single-cylinder, and four-stroke motor, is used. The RNG k-Epsilon coupled to power-law combustion models is applied to describe the complex in-cylinder turbulent reacting flow, while the hybrid Eulerian-Lagrangian Kelvin Helmholtz-Rayleigh Taylor (KH-RT) spray model is employed to capture the spray breakup. Third, highlight the impact of these surrogate fuels on the combustion properties along with the exergy of the engine. The results include distribution of temperature, pressure, heat release rate (HRR), vapor penetration length, and exergy efficiency. The effect of the surrogates on pollutant formation (NOX, CO, CO2) is also highlighted. The fifth surrogate showed 47% exergy efficiency. The fourth surrogate agreed well with the maximum experimental pressure, which equaled 85 Mpa. The first, second, and third surrogates registered 400, 316, and 276 g/kg fuel, respectively, of the total CO mass fraction at the outlet. These quantities were relatively higher compared to the fourth and fifth RMs.     

Structural properties of new spiro-1,3-propanediaminocyclotriphosphazene derivatives

New 1,3-propanediaminocyclotriphosphazene derivatives (7-17) were synthesized from the reactions of spiro-1,3-propanediaminocyclotriphosphazene, N₃P₃Cl₄[NH(CH₂)₃NH] (1) with the cyclopropanemethylamine (2), cyclohexylamine (3), pyrrolidine (4) cyclohexanol (5), cyclopropylmethanol (6). The structures of the novel compounds (7-17) were characterized by elemental analysis, mass spectrometry, ¹H and ³¹P NMR spectroscopy. The molecular structures of 8, 12 and 13 were determined by X-ray crystallography. The structures of all these three compounds are in the monoclinic crystal system; compounds 8 and 12 have the P21/c space group while compound 13 has the P21/n space group. The ring conformation of the cyclotriphosphazene and other external rings were investigated based on the X-ray crystal structures.