Origin of rate enhancement and asynchronicity in iminium catalyzed Diels–Alder reactions

The Diels–Alder reactions between cyclopentadiene and various α,β-unsaturated aldehyde, imine, and iminium dienophiles were quantum chemically studied using a combined density functional theory and coupled-cluster theory approach. Simple iminium catalysts accelerate the Diels–Alder reactions by lowering the reaction barrier up to 20 kcal mol⁻¹ compared to the parent aldehyde and imine reactions. Our detailed activation strain and Kohn–Sham molecular orbital analyses reveal that the iminium catalysts enhance the reactivity by reducing the steric (Pauli) repulsion between the diene and dienophile, which originates from both a more asynchronous reaction mode and a more significant polarization of the π-system away from the incoming diene compared to aldehyde and imine analogs. Notably, we establish that the driving force behind the asynchronicity of the herein studied Diels–Alder reactions is the relief of destabilizing steric (Pauli) repulsion and not the orbital interaction between the terminal carbon of the dienophile and the diene, which is the widely accepted rationale.

Quantum chemical activation strain analyses revealed that iminium catalysts accelerate Diels–Alder reactions by reducing the Pauli repulsion between reactants.     

Study of the morphology of a laser-produced aerosol plume by cavity ringdown laser absorption spectroscopy

Cavity ring-down laser absorption spectroscopy (CRLAS) was applied for the first time to detection and characterization of laser breakdown generated aerosols. The method provided time-resolved morphological information on the aerosol plume, which is of importance in laser ablation (LA) and deposition, in laser-induced breakdown spectroscopy (LIBS) analysis, and in laser ablation inductively coupled plasma (LA-ICP) methods. This method provides sensitive detection of a variety of aerosols produced under ambient conditions. The morphological investigation revealed that the aerosol density has a reproducible pattern as a function of distance from the surface, although its details depend on time, on geometrical parameters and on the surface characteristics.     

Pairing of propellers: dimerization of octahedral ruthenium(II) and osmium(II) complexes of eilatin via pi-pi stacking featuring heterochiral recognition

Five octahedral eilatin complexes of the type [M(L-L)(2)(eilatin)](2+) (M = Ru, Os; L-L = bipyridyl-type ligands) were synthesized, and their dimerization via pi-pi stacking was studied by crystallography and (1)H NMR techniques. The X-ray structures of these racemic complexes were solved and revealed that the eilatin complexes are organized as discrete dimers in which the eilatin residues of each complex are stacked in centrosymmetric packing. Chemical shift dependence on concentration in the (1)H NMR spectra support fast dimer-monomer equilibrium, and the structures of the dimers in acetonitrile solution are proposed to be analogous to their solid-state structures. Dimerization constants in acetonitrile were measured for the five racemic eilatin complexes that exhibit different structural parameters, as well as for the two enantiomeric forms of one of these complexes. They were found to be independent of the metal (Ru vs Os), strongly dependent on the steric effects introduced by the L-L ligands (2,2'-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 2,2'-biquinoline), and dependent on the optical purity of the complexes. A clear preference for heterochiral over homochiral dimer formation was demonstrated. This is the first report of chiral recognition in solution, exhibited by simple chemical systems held solely by pi-stacking interactions.     

Comparison of UV and visible Raman spectroscopy of bulk metal molybdate and metal vanadate catalysts

The visible (532 and 442 nm) and UV (325 nm) Raman spectra of bulk mixed metal oxides (metal molybdates and metal vanadates) were compared on the same spectrometer, for the first time, to allow examination of how varying the excitation energy from visible to UV affects the resulting Raman spectra. The quality of the Raman spectra was found to be a strong function of the absorption properties of the bulk mixed oxide. For bulk mixed metal oxides that absorb weakly in the visible and UV regions, both the visible and UV Raman spectra were of high quality and exhibit identical vibrational bands, but with slightly different relative intensities. For bulk mixed metal oxides that absorb strongly in the UV and visible regions and/or strongly in the UV and weakly in the visible regions, the visible Raman spectra are much richer in structural information and of higher resolution than the corresponding UV Raman spectra. This is a consequence of the strong UV absorption that significantly reduces the sampling volume and number of scatterers giving rise to the Raman signal. The shallower escape depth of UV Raman, however, was not sufficient to detect vibrations from the surface metal oxide species that are present on the outermost surface layer of these crystalline mixed metal oxide phases as previously suggested. It was also demonstrated that there is no sample damage by the more energetic UV excitation when very low laser powers and fast detectors are employed, thus avoiding the need of complicated fluidized bed sample arrangements sometimes used for UV Raman investigations. The current comparative Raman investigation carefully documents, for the first time, the advantages and disadvantages of applying different excitation energies in collecting Raman spectra of bulk mixed metal oxide materials.     

Sandwich-type phosphotungstates: structure,electrochemistry, and magnetism of the trinickel-substituted polyoxoanion [Ni(3)Na(H(2)O)(2)(PW(9)O(34))(2)](11-)

The novel nickel-substituted, dimeric phosphotungstate [Ni(3)Na(H(2)O)(2)(PW(9)O(34))(2)](11-) (1) has been synthesized and characterized by IR spectroscopy, elemental analysis, and electrochemistry. X-ray single-crystal analysis was carried out on Na(11)[Ni(3)Na(H(2)O)(2)(PW(9)O(34))(2)].21.25H(2)O, which crystallizes in the triclinic system, space group P1, with a = 12.2467(6) A, b = 16.6031(7) A, c = 22.4017(12) A, alpha = 73.9870(10) degrees, beta = 87.6060(10) degrees, gamma = 79.344(2) degrees, and Z = 2. The polyanion consists of two lacunary B-alpha-[PW(9)O(34)](9-) Keggin moieties linked via three nickel(II) centers and a sodium ion. The structure of 1 is composed of two fused Keggin fragments that represent different Baker-Figgis isomers (alpha- vs beta-type). Electrochemical studies show that 1 exhibits a stable and reproducible voltammetric pattern, with a first wave featuring a chemically reversible four-electron/four-proton process. An investigation of the magnetic properties indicates that the three nickel centers exhibit ferromagnetic exchange interaction.     

Anti-Pathogenic Properties of the Combination of a T3SS Inhibitory Halogenated Pyrrolidone with C-30 Furanone

Antimicrobial resistance is one of the current public health challenges to be solved. The World Health Organization (WHO) has urgently called for the development of strategies to expand the increasingly limited antimicrobial arsenal. The development of anti-virulence therapies is a viable option to counteract bacterial infections with the possibility of reducing the generation of resistance. Here we report on the chemical structures of pyrrolidones DEXT 1–4 (previously identified as furan derivatives) and their anti-virulence activity on Pseudomonas aeruginosa strains. DEXT 1–4 were shown to inhibit biofilm formation, swarming motility, and secretion of ExoU and ExoT effector proteins. Also, the anti-pathogenic property of DEXT-3 alone or in combination with furanone C-30 (quorum sensing inhibitor) or MBX-1641 (type III secretion system inhibitor) was analyzed in a model of necrosis induced by P. aeruginosa PA14. All treatments reduced necrosis; however, only the combination of C-30 50 µM with DEXT-3 100 µM showed significant inhibition of bacterial growth in the inoculation area and systemic dispersion. In conclusion, pyrrolidones DEXT 1–4 are chemical structures capable of reducing the pathogenicity of P. aeruginosa and with the potential for the development of anti-virulence combination therapies.     

On the Stability of a Laminar Wall Jet with Heat Transfer

The hydrodynamic stability of a low speed, plane, non-isothermal laminar wall jet at a constant temperature boundary condition was investigated theoretically and experimentally. The mean velocity and temperature profiles used in the stability analysis were obtained by implementing the Illingworth–Stewartson transformation that allows one to extend the classical Glauert solution to a thermally non-uniform flow. The stability calculations showed that the two unstable eigenmodes coexisting at moderate Reynolds numbers are significantly affected by the heat transfer. Heating is destabilizing the flow while cooling is stabilizing it. However, the large-scale instabilities associated with the inflection point of the velocity profile still amplify in spite of the high level of the stabilizing temperature difference. The calculated stability characteristics of the wall jet with heat transfer were compared with experimental data. The comparison showed excellent agreement for small amplitudes of the imposed perturbations. The agreement is less good for the phase velocities of the sub-harmonic wave and this is attributed to experimental difficulties and to nonlinear effects.     

Imploding stars,shifting continents,and the inconstancy of matter

Two revolutionary concepts of the twentieth century—continental drift and the existence of superdense stars and black holes—had extended histories which ran in curious parallel for five decades. Between the wars each encountered a fierce and emotionally charged resistance which may have had a common psychological root. Each threatened man's instinctive faith in the permanence of matter.Work supported by Canadian Institute for Advanced Research and by NSERC of Canada.