N‐(Tri­phenyl­methyl­sulfanyl)­phthal­imide

The title compound, C₂₇H₁₉NO₂S, contains chains of fused (19) rings formed by intermolecular C—H·O=C hydrogen bonds and running along the [011] and [01] directions. These chains are linked through short intermol­ecular C—H·π contacts, giving rise to sheets. The conformation of the title compound is dominated primarily by the nearly orthogonal lone‐pair orbitals on the N and S atoms.     

The consistency index in reciprocal matrices: Comparison of deterministic and statistical approaches

When checking the inconsistency level of a positive reciprocal matrix Saaty uses a deterministic criterion based on two parameters, a benchmark (the average), and a consistency level, usually 10%. Using results from a simulation experiment with 100,000 positive random reciprocal matrices of size varying from 3 to 15, we developed a probabilistic criterion and compare it to Saaty’s index. We found that if a positive reciprocal matrix is consistent according to the deterministic criterion is also consistent according to the probabilistic criterion only if we accept a higher than usual probability of Type I error. Reducing this error implies that the benchmark must be a small percentile of the probability distribution of the consistency index.     

Nitric oxide-dependent pigment migration induced by ultraviolet radiation in retinal pigment cells of the crab Neohelice granulata

The purpose of this study was to verify the occurrence of pigment dispersion in retinal pigment cells exposed to UVA and UVB radiation, and to investigate the possible participation of a nitric oxide (NO) pathway. Retinal pigment cells from Neohelice granulata were obtained by cellular dissociation. Cells were analyzed for 30 min in the dark (control) and then exposed to 1.1 and 3.3 J cm⁻² UVA, 0.07 and 0.9 J cm⁻² UVB, 20 n m β-PDH (pigment dispersing hormone) or 10 μ m SIN-1 (NO donor). Histological analyses were performed to verify the UV effect in vivo . Cultured cells were exposed to 250 μ m L-NAME (NO synthase blocker) and afterwards were treated with UVA, UVB or β-PDH. The retinal cells in culture displayed significant pigment dispersion in response to UVA, UVB and β-PDH. The same responses to UVA and UVB were observed in vivo . SIN-1 did not induce pigment dispersion in the cell cultures. l-NAME significantly decreased the pigment dispersion induced by UVA and UVB but not by β-PDH. All retinal cells showed an immunopositive reaction against neuronal nitric oxide synthases. Therefore, UVA and UVB radiation are capable of inducing pigment dispersion in retinal pigment cells of Neohelice granulata and this dispersion may be nitric oxide synthase dependent.     

Theoretical study on the chemical fate of adducts formed through free radical addition reactions to carotenoids

It is well known that free radicals are responsible for oxidative stress and cause numerous health disorders. As a result, the study of molecules that can scavenge free radicals is significant. One of the most important classes of free radical scavengers are carotenoids (CAR). In this work, the effectiveness of the CAR in terms of the radical adduct formation (RAF) reaction is studied using density functional theory calculations (in polar and non-polar environments). The reactions between four CAR [β-carotene (BC), zeaxanthin (ZEA), canthaxanthin (CANTA) and astaxanthin (ASTA)] with eight different radicals (^?OH, ^?OOH, ^?CH₃, ^?O–CH₃, ^?OO–CH₃, ^?SH, ^?O–CH₂–CH=CH₂, and ^?OO–CH₂–CH=CH₂), as well as substantial further reactions involved in the radical chain propagation, are analyzed. According to our results, the RAF reactions are controlled to a larger extent by the nature of the free radical than by the particular CAR they are reacting with. Thermochemistry calculations predict that each CAR molecule is able to scavenge at least two free radicals, which would lead to the termination of the radical chain process. Epoxy and diepoxy CAR species can be formed, being epoxy molecules as good free radical scavengers as their parent CAR. ASTA and CANTA are predicted to be less reactive, when reacting through RAF mechanism, than BC and ZEA.     

Aggregation of a Distributed Source in Morphogen Gradient Formation

In the development of a biological entity, ligands (such as Decapentaplegic (Dpp) along the anterior–posterior axis of the Drosophila wing imaginal disc) are synthesized at a localized source and transported away from the source for binding with cell surface receptors to form concentration gradients of ligand–receptor complexes for cell signaling. Generally speaking, activities such as diffusion and reversible binding with degradable receptors also take place in the region of ligand production. The effects of such morphogen activities in the region of localized distributed ligand source on the ligand–receptor concentration gradient in the entire biological entity have been modeled and analyzed as System F in [ 1 ]. In this paper, we deduce from System F, a related end source model (System A) in which the effects of the distributed ligand source is replaced by an idealized point stimulus at the border between the (posterior) chamber and the ligand production region that simulates the average effects of the ligand activities in the production zone. This aggregated end source model is shown to adequately reproduce the significant implications of System F and to contain the corresponding ad hoc point source model, System R of [ 2 ], as a special case. Because of its simpler mathematical structure and the absence of any limitation on the ligand synthesis rate for the existence of steady-state gradients, System A type models are expected to be used widely. An example of such application is the recent study of the inhibiting effects of the formation of nonsignaling ligand–nonreceptor complexes [ 3 ].     

On the origin of the hole pressure

Summary One wall of a slit die apparatus contains a slot filled with the test liquid. Photographs of marked streamlines near the slot mouth show a pronounced curvature. A 0.5% aqueous solution of Separan AP 30 and molten polystyrene and polyethylene were investigated at low values of Reynolds number (Re < 1.0). In each case, streamlines are convex towards the slot mouth. This supports the hypothesis ofTanner andPipkin which attributes hole pressures in flowing viscoelastic liquids to the combined effect of holegenerated streamline curvature and shear-generated normal stress differences.

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Zusammenfassung In einer der Wände einer Schlitzdüsenvorrichtung ist eine mit Testflüssigkeit gefüllte Quernut angebracht. Es wurde die Strömung einer 0,5%-igen wässerigen Separan AP 30-Lösung, sowie einer Polystyrol- und einer Polyäthylenschmelze bei kleinen Reynoldszahlen (Re < 1.0) untersucht. In allen Fällen waren die Stromlinien konvex, also zur Schlitzmündung hin gekrümmt. Dadurch wird die Hypothese vonTanner andPipkin unterstützt, wonach die Lochdrücke in strömenden viskoelastischen Flüssigkeiten als Wirkung der durch die Scherung erzeugten Normalspannungsdifferenzen auf die gekrümmten Stromlinien erklärt werden.

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Department of Engineering Mechanics.

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Material Science Program.

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With 4 figures     

Flow development of xanthan solutions in capillary rheometers

Flow experiments through capillaries with 0.2% xanthan in aqueous solution and 0.1 N NaCl brine were carried out to study the influence of the molecular conformation on the flow development at relatively low shear rates, from 20s^–1 to 400s^–1. Capillaries with a wide range of length-to-diameter ratios, L/D = 4.5 to 1015 were used.The apparent viscosity as a function of L/D at a constant shear rate shows a continuous decrement of the viscosity as L/D increases, until an asymptotic value is reached. The decrement in the apparent viscosity is partially explained in terms of slip. It was found that slip is a function of L/D as well as shear stress, i.e., slip develops during flow, thus inducing spatial anisotropy in the fluid until a stable state is reached. However, the substantial difference in apparent viscosity between short capillaries and capillaries longer than 300 D may be attributed to dominant elongational flow due to the contraction in the small capillaries and slip in long capillaries.The flow in a sufficiently long capillary can be divided in four regions rather than three, as is usually assumed. In the first region, which corresponds to the entry, elongational and shear flow coexist and elongational flow dominant. In the second region, end effects and slip development are coupled. In the third region the flow is fully developed and end effects are negligible. However, the fluid shows physical characteristics different from those of the fluid at rest, as a consequence of prior slip development. The fourth zone is the exit region in which the velocity rearranges due to the change of boundary conditions. The length of each region depends on the conformation of the macromolecules and shear rate. In addition, it was found that the stiffness of xanthan increases with the increase of the ionic strength.Finally, a performance of Bagley's analysis in the whole range of L/D studied showed that the use of the Bagley correction is not a reliable way to correct for end effects when the flow is not fully developed and/or in the presence of slip.Dedicated to Arthur S. Lodge at the occasion of his 70th birthday and his retirement from the University of Wisconsin.