Nanometer thin-film Ni-NiO-Ni diodes for 30 THz radiation

We report on the development of antenna-coupled thin-film nanometer Ni-NiO-Ni diodes which are used to detect 10.6 m CO₂-laser radiation. The Ni-NiO-Ni diodes have a minimum contact area of 0.056 m². This is smaller than those of any previously fabricated thin-film Metal-metalOxide-Metal (MOM) diodes. By measuring the second derivative of the dc current-voltage characteristics I(V), we demonstrate that the nonlinearity of the dc I(V) characteristics of our Ni-NiO-Ni diodes is larger than that of the dc I(V) characteristics of thin-film MOM diodes fabricated before by other authors. It is comparable to the nonlinearity of the dc I(V) characteristics of point-contact MOM diodes. Furthermore, we show that the polarisation-dependent infrared response of the Ni-NiO-Ni diodes is due to antenna coupling and that the polarisation-independent response is mainly of thermal origin. Consequently, the heating of the Ni-NiO-Ni diodes is due to the absorption of the incident CO₂-laser radiation in the SiO₂, and dissipation of the laser-induced ac antenna currents in the antenna.     

Bioinspired Intervertebral Disc with Multidirectional Stiffness Prepared via Multimaterial Additive Manufacturing

Degenerative disc disease (DDD) has become a significant public health issue worldwide. This can result in loss of spinal function affecting patient health and quality of life. Artificial total disc replacement (A-TDR) is an effective approach for treating symptomatic DDD that compensates for lost functionality and helps patients perform daily activities. However, because current A-TDR devices lack the unique structure and material characteristics of natural intervertebral discs (IVDs), they fail to replicate the multidirectional stiffness needed to match physiological motions and characterize anisotropic behavior. It is still unclear how the multidirectional stiffness of the disc is affected by structural parameters and material characteristics. Herein, a bioinspired intervertebral disc (BIVD-L) based on a representative human lumbar segment is developed. The proposed BIVD-L reproduces the multidirectional stiffness needed for the most common physiological kinematic behaviors. The results demonstrate that the multidirectional stiffness of the BIVD-L can be regulated by structural and material parameters. The results of this research deepen knowledge of the biomechanical behavior of the human lumbar disc and may provide new inspirations for the design and fabrication of A-TDR devices for both engineering and functional applications.     

Asymmetric synthesis of unsaturated, fused bicyclic proline analogues through amino alkylation of cyclic bis(allylsulfoximine)titanium complexes and migratory cyclization of delta-amino alkenyl aminosulfoxonium salts

Described is an asymmetric synthesis of new Delta(3a,4)-unsaturated, fused bicyclic proline analogues from cyclic bis(allylsulfoximine)titanium complexes and N-tert-butylsulfonyl imino ethyl ester. Treatment of the enantiomerically pure five-, six-, seven-, and eight-membered cyclic bis(allylsulfoximine)titanium complexes with the imino ester gave mixtures of the corresponding (E,syn)- and (Z,syn)-configured, delta-sulfoximine substituted, cyclic gamma,delta-unsaturated alpha-amino acid esters with high regio- and diastereoselectivities in good yields. Activation of the N-methyl sulfoximine group of these amino acid derivatives through methylation with Me(3)OBF(4) afforded in nearly quantitative yields the corresponding (dimethylamino)sulfoxonium salts. A novel migratory cyclization of these salts with DBU gave via an isomerization to the corresponding allylic (dimethylamino)sulfoxonium salts and an intramolecular substitution of the (dimethylamino)sulfoxonium group the enantio- and diastereomerically pure, bicyclic, N-tert-butylsulfonyl protected proline analogues having a six- and eight-membered unsaturated carbocyclic ring. Cyclization of the alkenyl (dimethylamino)sulfoxonium salts was independent of the configuration of the double bond. N,N-Dimethylphenylsulfinamide of > or =99% ee was obtained in good yield as a further reaction product. Conversion of the sulfinamide to N,S-dimethyl-S-phenylsulfoximine of > or =99% ee, the starting material for the synthesis of the allylic sulfoximines, had been accomplished previously. Finally, cleavage of the tert-butylsulfonyl protecting group with anhydrous acid furnished the fused bicyclic proline analogue containing an unsaturated six-membered ring in high yield.     

The insertion of the dioxides of carbon and sulphur into the palladium-carbon bond

Bis ( η¹, η²-allyl) palladium phosphine complexes react with carbon dioxide and sulphur dioxide by insertion into the palladium-carbon σ-bond to give η³-allylpalladium-carboxylate and -S-sulphinate complexes.     

Paracrystalline order in polymers

Summary A brief review of one and three dimensional models of paracrystalline superstructures in polymers, as used for analysing the small angle scattering, is given.

---

Zusammenfassung Es wird ein knapper überblick über die bei der Analyse der Kleinwinkelstreuung von Polymeren verwendeten einund dreidimensionalen Modelle der Überstruktur gegeben.

     

On the separation of initial and final state effects in photoelectron spectroscopy using an extension of the auger-parameter concept

First, we show that the quantity Δβ(i) = ΔE_A(kii) + 2ΔE_B(i) — ΔE_B(k) is directly related to the final state relaxation contribution ΔE_R(i) of the binding energy shift ΔE_B(i). ΔE_A(kii) is the kinetic energy shift of the Auger transition which corresponds to the decay of a hole state with a hole in level k into a final state with two holes in level i. The shift parameter Δβ(i), which is based on information on two binding energies, is conceptually similar to Wagner's Auger parameter. To establish the relation between Δβ(i) and ΔR(i) one needs, however, less drastic approximations than in the case of Auger parameter shifts. The only approximation necessary is the assumption that ΔR(i) is determined by coulomb contributions.Secondly, we use Δβ (i) to analyse the experimental data of eighteen gaseous phosphorus-containing compounds obtained by Sodhi and Cavell¹. It is shown that ΔR(P_2p) is strongly related to changes in the polarizability of the ligands. The initial state effects derived from our study deviate from those expected on the basis of simple electronegativity considerations.     

Understanding supported reactions in spherical compartments: a general algorithm to model and determine rate constants, diffusion coefficients, and spatial product distributions

A general algorithm allowing the numerical modeling of the time and space dependence of product formation in spherical reaction volumes is described. The algorithm is described by the complete set of mass balance equations. On the basis of these equations, the effects of the diffusion coefficient, reaction rate, bead size, reagent excess, and packing density of the resin beads on the overall reaction rates are determined for second-order reactions. Experimental data of reaction progress are employed to calculate reaction rates and diffusion coefficients in polymer-supported reactions. In addition, the conditions for shell-like product formation are determined, and various strategies for the radial patterning of resin beads are compared. The effect of diffusion on polymer-supported enzyme-catalyzed reactions of the Michaelis-Menten type is treated, as well. Finally, the effects of typical nonideal solid-phase phenomena, namely, the inhomogeneity of rate constants and the concentration dependence of diffusion coefficients, on overall rates are discussed.