Synthesis and catalytic activity of new chiral unsymmetrical Mn(III)-Schiff-base complexes containing salicylaldehyde and 1-(2-hydroxyphenyl)ketone units

Two new chiral unsymmetrical (non-C₂-symmetric) Schiff-base ligands containing salicylaldehyde and 1-(2-hydroxyphenyl)ketone units were synthesized from (R,R)-1,2-diphenylethylenediamine as the chiral diamine using a stepwise approach. The Mn(III) complexes of the ligands were subsequently used as catalysts in asymmetric epoxidation of unfunctionalized alkenes and the results were compared with those obtained using typical C₂-symmetric Mn(III)–salen complexes. Possible reasons for the differences in reactivity and selectivity between the two types of catalysts are briefly discussed.     

On string topology of classifying spaces

Let G be a compact Lie group. By work of Chataur and Menichi, the homology of the space of free loops in the classifying space of G is known to be the value on the circle in a homological conformal field theory. This means in particular that it admits operations parameterized by homology classes of classifying spaces of diffeomorphism groups of surfaces. Here we present a radical extension of this result, giving a new construction in which diffeomorphisms are replaced with homotopy equivalences, and surfaces with boundary are replaced with arbitrary spaces homotopy equivalent to finite graphs. The result is a novel kind of field theory which is related to both the diffeomorphism groups of surfaces and the automorphism groups of free groups with boundaries. Our work shows that the algebraic structures in string topology of classifying spaces can be brought into line with, and in fact far exceed, those available in string topology of manifolds. For simplicity, we restrict to the characteristic 2 case. The generalization to arbitrary characteristic will be addressed in a subsequent paper.     

Ultraviolet B irradiation affects resistance of rainbow trout (Oncorhynchus mykiss) against bacterium Yersinia ruckeri and trematode Diplostomum spathaceum

Ultraviolet B (UVB) radiation is known to have various effects on the immune system of fish, but the effect on the actual disease resistance has remained largely unknown. Here we studied the effect of UVB on the resistance of rainbow trout (Oncorhynchus mykiss) against a bacterium Yersinia ruckeri, the causative agent of enteric red mouth disease, and a trematode parasite Diplostomum spathaceum, which causes cataracts in fish. The fish were exposed to UVB irradiation seven times in 14 days, and inoculated intraperitoneally with Y. ruckeri on day 5 after the first irradiation. On day 2 postinfection (p.i.), the number of viable bacteria in the kidney was lower in UVB-exposed than in unexposed fish. However, on day 8 p.i., UVB-irradiated fish had not been able to clear remaining Y. ruckeri effectively, and had a slightly higher bacterial load than controls. A similar, although not significant, effect was seen in the bacterial numbers in spleen. In the other experiment, fish were exposed to UVB for six consecutive days and then exposed to D. spathaceum. A significantly higher number of parasites was detected in the eyes of irradiated fish, indicating reduced resistance against the pathogen. Furthermore, UVB-irradiation altered the immunological and hematological parameters of fish, which also verified the immunomodulatory potential of UVB in the present study.     

Logic as a Science and Logic as a Theory: Remarks on Frege, Russell and the Logocentric Predicament

Since its publication in 1967, van Heijenoort??s paper, ??Logic as Calculus and Logic as Language?? has become a classic in the historiography of modern logic. According to van Heijenoort, the contrast between the two conceptions of logic provides the key to many philosophical issues underlying the entire classical period of modern logic, the period from Frege??s Begriffsschrift (1879) to the work of Herbrand, G?del and Tarski in the late 1920s and early 1930s. The present paper is a critical reflection on some aspects of van Heijenoort??s thesis. I concentrate on the case of Frege and Russell and the claim that their philosophies of logic are marked through and through by acceptance of the universalist conception of logic, which is an integral part of the view of logic as language. Using the so-called ??Logocentric Predicament?? (Henry M. Sheffer) as an illustration, I shall argue that the universalist conception does not have the consequences drawn from it by the van Heijenoort tradition. The crucial element here is that we draw a distinction between logic as a universal science and logic as a theory. According to both Frege and Russell, logic is first and foremost a universal science, which is concerned with the principles governing inferential transitions between propositions; but this in no way excludes the possibility of studying logic also as a theory, i.e., as an explicit formulation of (some) of these principles. Some aspects of this distinction will be discussed.     

One-pot synthesis of [2+2]-helicate-like macrocycle and 2+4-μ4-oxo tetranuclear open frame complexes: Chiroptical properties and asymmetric oxidative coupling of 2-naphthols

Synthesis of binuclear Cu(II) terminally closed [ 2+2 ]- double-stranded helicate-like macrocycles 1, 1′ , 1″ , 2 , 2′ , 2″ and 2+4- μ₄-oxo tetranuclear open frame complexes 3 , 3′ , 3″ , 4 , 4′ , 4″ are established. Adapting one-pot self-assembly technique from simple three components systems: 1,1′-binaphthyl-2,2′-diamine, 4-methyl-2,6-diformyl phenol and cupric salts, the helicate-like [ 2+2 ]- macrocyclic complexes 1–1″, 2–2″ and 2+4- μ₄-oxo tetranuclear complexes 3–3″ , 4–4″ were obtained by appropriately altering the reaction condition such as temperature and subcomponent ratio. Density Functional Theory (DFT) calculations were carried out for understanding the structural geometries, intermediates involved in the diverse formation of [ 2+2 ] and 2+4 frameworks. The single crystal X-ray structures obtained for 1′ , 2 and 3 confirms the self-assembly process in line with DFT. This detailed analysis tempted us to derive a plausible mechanism for this long standing challenge in the synthesis of such macrocycles using 1,1′-binaphthyl-2,2′-diamine (BNDA) and aromatic aldehyde. The chiroptical properties of enantiopure complexes and their catalytic applications in asymmetric oxidative coupling of 2-naphthol to chiral 1,1’-Bi-2-naphthol (BINOL) achieved in good yield and ee were discussed.     

Predicting scattering properties of fiber suspensions using Mie theory and probabilistic cross-sectional diameter of fibers

Optical Review - Scattering of visible light by micrometer-scale natural wood fibers is usually treated by assuming fibers to be perfect long cylindrical scatterers. In industrial processes,...     

{2,2′‐[(R,R)‐Cyclo­hexane‐1,2‐diyl­bis(nitrilo­methyl­idyne)]­bis[6‐tert‐butyl‐4‐(tri­phenyl­phosphonio­methyl)­phenol­ato]‐O,N,N′,O′}copper(II) dichloride hexakis­(deutero­chloro­form) solvate

The title compound, [Cu(C₆₆H₆₈N₂O₂P₂)]Cl₂·6CDCl₃, consists of complex cations, chloride ions and deutero­chloro­form solvate mol­ecules. The complex cation crystallizes in two different conformations. In both cases, Cu^II ions lie on twofold axes and the geometry around them is slightly distorted square planar. The dihedral angles between the N/Cu/N and O/Cu/O planes are 5.6 (9) and 3.9 (10)° for mol­ecules A and B, respectively.     

Good-Practice Non-Radioactive Assays of Inorganic Pyrophosphatase Activities

Inorganic pyrophosphatase (PPase) is a ubiquitous enzyme that converts pyrophosphate (PP_i) to phosphate and, in this way, controls numerous biosynthetic reactions that produce PP_i as a byproduct. PPase activity is generally assayed by measuring the product of the hydrolysis reaction, phosphate. This reaction is reversible, allowing PP_i synthesis measurements and making PPase an excellent model enzyme for the study of phosphoanhydride bond formation. Here we summarize our long-time experience in measuring PPase activity and overview three types of the assay that are found most useful for (a) low-substrate continuous monitoring of PP_i hydrolysis, (b) continuous and fixed-time measurements of PP_i synthesis, and (c) high-throughput procedure for screening purposes. The assays are based on the color reactions between phosphomolybdic acid and triphenylmethane dyes or use a coupled ATP sulfurylase/luciferase enzyme assay. We also provide procedures to estimate initial velocity from the product formation curve and calculate the assay medium’s composition, whose components are involved in multiple equilibria.     

A careful look at the importance of criteria and weights

We investigate the connection between weights, scales, and the importance of criteria, when a linear value function is assumed to be a suitable representation of a decision maker’s preferences. Our considerations are based on a simple two-criteria experiment, where the participants were asked to indicate which of the criteria was more important, and to pairwise compare a number of alternatives. We use the participants’ pairwise choices to estimate the weights for the criteria in such a way that the linear value function explains the choices to the extent possible. More specifically, we study two research questions: (1) is it possible to find a general scaling principle that makes the rank order of the importance of criteria consistent with the rank order of the magnitudes of the weights, and (2) how good is a simple, direct method of asking the decision maker to “provide” weights for the criteria compared to our estimation procedure. Our results imply that there is reason to question two common beliefs, namely that the values of the weights would reflect the importance of criteria, and that people could reliably “provide” such weights without estimation.     

Controllability method for acoustic scattering with spectral elements

We formulate the Helmholtz equation as an exact controllability problem for the time-dependent wave equation. The problem is then discretized in time domain with central finite difference scheme and in space domain with spectral elements. This approach leads to high accuracy in spatial discretization. Moreover, the spectral element method results in diagonal mass matrices, which makes the time integration of the wave equation highly efficient. After discretization, the exact controllability problem is reformulated as a least-squares problem, which is solved by the conjugate gradient method. We illustrate the method with some numerical experiments, which demonstrate the significant improvements in efficiency due to the higher order spectral elements. For a given accuracy, the controllability technique with spectral element method requires fewer computational operations than with conventional finite element method. In addition, by using higher order polynomial basis the influence of the pollution effect is reduced.