(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Synthesis and Diels-Alder Reactions of a New Kind of Chiral Dienophiles: Cyclic Vinyl-p-tolylsulfilimines

A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.     

Inverse Hall–Petch effect in nanostructured ZnS

Vickers microhardness of compacted nanoparticles of ZnS of average grain sizes 3–12 nm was studied for different compaction pressures. The hardness was found to increase rapidly with load for smaller values of the load and then to become practically independent of load. The microhardness was found to increase with increase in grain size showing inverse Hall–Petch relation in the present study.     

Dopant concentration dependent magnetism of Cu-doped TiO2 nanocrystals

Journal of Nanoparticle Research - Mannosylation is a method commonly used to deliver nanomaterials to specific organs and tissues via cellular macrophage uptake. In this work, for the first time,...     

Causal loop diagrams as a de-escalation technique

Escalation of commitment, the tendency of decision makers to keep on investing in losing courses of action, has been shown to be a costly decision bias that affects many areas of decision making. Even though escalation is a widely studied phenomenon, there has been comparatively little research on how to avoid this bias. The present study focuses on de-escalation of commitment and proposes that causal loop diagrams (CLDs) can help to decrease escalating commitment to a failing course of action. By means of an experiment, this study shows that using a CLD decreases escalation tendencies.     

Phase diagrams of lyotropic cholesteric fluids

Experimental investigations of lyotropic cholesterics fluids are presented which show that changes in the shape anisotropy and chirality of the micellar population determine the topology of the temperature-concentration phase diagrams. For given amounts of the substances which induce the chirality and modify the shape anisotropy of the micelles, two distinct biaxial cholesteric phases are disclosed in the phase diagrams. This is interpreted in the framework of the catastrophe theory of phase transitions.     

Electronic Structure of Nanostructured Nickel Oxide Using Ni 2p XPS Analysis

We examine the electronic structure of nanostructured nickel oxide with an average particle size of 4–5nm using Ni 2p X-ray photoelectron spectrum. The most striking features of the spectrum are the Ni 2p main line broadening and an increase in the relative intensity of the 1.5eV satellite. We explain the observations as due to an enhancement in the non-local screening process on the basis of Ni₇O₃₆ cluster model by taking into account the large surface area to volume ratio and high Ni²⁺ vacancy concentration in nanostructured nickel oxide. The important contribution of an enhanced Ni 3d–O 2p hybridization and the origin of shake-up peaks above the 7eV satellite is also discussed. The study underlines the importance of factors such as the actual local environment of the core hole site, defect density and distribution, possible structural transitions, etc. in determining the Ni 2p core level X-ray photoelectron spectrum of nanostructured nickel oxide and shows that the actual synthesis routes and the thermal history greatly influence the electronic structure of nanostructured nickel oxide.