Kohlenwasserstoffe

Analytical and Bioanalytical Chemistry -     

Ab initio structural investigation of methyl and ethyl carbamate, and carbamyl choline

The molecular structures of four conformations of methylcarbamate, three forms of ethylcarbamate, four forms of ethylacetate, and of the trans-form of carbamylcholine, were determined by ab initio gradient geometry refinement on the 4-21G level, and the results are compared with the geometries of homologous systems. Significant changes in bond distances and angles are observed with torsional changes, but, barring long-range non-bonded interactions, they are to a large extent localized in that part of the system which is directly involved with the torsional transition; i.e., through-bond effects in a bond distance chain begin to be insignificant after a sequence of three bonds.     

An extended parabolic equation and its application to the calculation of transverse and longitudinal mutual coherence functions in atmospheric turbulence

An extended, wide forward angle scattering version of the parabolic equation is considered and an operator expression for the solution of the generalized nmth moment of the electromagnetic wave field is obtained. Here, 'generalized' connotes the consideration of both the transverse as well as the longitudinal spatial moments of the wave field. A unified solution for the generalized second-order moment, i.e. the mutual coherence function (MCF), is found. The solution is applied to the case of Kolmogorov turbulent fluctuations within the atmosphere. In addition to demonstrating an interesting decaying oscillatory behaviour of the longitudinal MCF in atmospheric turbulence, it is found that the use of the extended parabolic equation yields negligible corrections to the transverse MCF, as calculated from the parabolic equation in the paraxial approximation.     

Supramolecular Diblock Copolymers Featuring Well‐defined Telechelic Building Blocks

We report supramolecular AB diblock copolymers comprised of well‐defined telechelic building blocks. Helical motifs, formed via reversible addition‐fragmentation chain‐transfer (RAFT) or anionic polymerization, are assembled with coil‐forming and sheet‐featuring blocks obtained via atom‐transfer radical polymerization (ATRP) or ring‐opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal‐coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π‐stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self‐assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug‐and‐play approach to fabricate hybrid π‐sheet/helix, π‐sheet/coil, and helix/coil architectures via directional self‐assembly.     

Determination of residual-stress variation with depth by the hole-drilling method

The hole-drilling method is a residual-stress measurement technique in which a blind hole (usually 1.6 mm or 3.2 mm in diameter) is drilled into a material and the strain perturbances around the hole are measured by surfacemounted strain gages. The conventional hole-drilling-method procedure is to analyze the net strain changes due to the drilling of the full-depth hole (usually about 100 percent of hole diameter) and to interpret the resulting stress calculations insofar as they represent the average stresses through the hole depth. It has been determined that this procedure may lead to significant errors, particularly where there are large stress variations through the hole depth. Such errors may be difficult to detect simply by observing the strain data. This paper describes a finite-element procedure which was used to develop calibration constants to allow measurements of residual-stress variation with depth to be routinely performed by the hole-drilling method.     

Introducing Intellectual Property in an Undergraduate Chemistry Curriculum

An exercise that introduces undergraduate chemistry majors to concepts associated with intellectual property is outlined. The assignment includes an introduction to the terminology associated with starting a company based on intellectual property and to nondisclosure agreements. After this, the students write a draft patent application. With over 150,000 United States patents issued annually, the role of intellectual property is prominent and becoming increasingly important in current corporations and in the formation of new businesses, as well as in government and academic settings.     

Numerical continuation of degenerate homoclinic orbits in planar systems

In this paper we develop numerical algorithms for the continuationof degenerate homoclinic connections in planar systems. We considerthe case where the equilibrium point has zero trace and twocases of higher-order degeneracies. The method we propose isable to continue homoclinic connections of order up to codimension-four.Application of the algorithm to four examples supports its validityand demonstrates its usefulness.