Kupferanalyse

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The curvature problem in general relativity

This essay investigates the relationships among the metric, the connection, the curvature, and the covariant curvature derivatives in general relativity. The extent to which the connection or the curvature together, possibly with certain curvature derivatives, determines the metric is considered, as well as other related problems. Some topological aspects of the problem are included and some applications to holonomy and symmetry groups are given.This article received honorable mention from the Gravity Research Foundation for 1987.     

Vinylferrocene homopolymer and copolymers: an electrochemical comparison.

Poly(vinylferrocene) (pVFc) homopolymer was synthesized by free radical polymerization, along with a series of pVFc-based copolymers containing either styrene, vinylanthracene or methylmethacrylate. This report details the electrochemical experiments conducted to examine the stability of the various pVFc based polymers, which is shown to be critically dependent on the extent of copolymerization. A trend was found that when the concentration of co-monomer was decreased, electrochemical stability was enhanced. Furthermore incorporation of a second monomer into the polymer chain produced a profound effect on the scan rate behaviour of the vinylferrocene moiety. As the concentration of co-monomer was decreased, the behaviour tended towards that of a diffusion controlled process. These results are of vital significance for the development of pVFc-based electrochemical sensors.     

Self-assembled low-molecular-weight gelator injectable microgel beads for delivery of bioactive agents

We report the preparation of hybrid self-assembled microgel beads by combining the low molecular weight gelator (LMWG) DBS-CONHNH₂ and the natural polysaccharide calcium alginate polymer gelator (PG). Microgel formulations based on LMWGs are extremely rare due to the fragility of the self-assembled networks and the difficulty of retaining any imposed shape. Our hybrid beads contain interpenetrated LMWG and PG networks, and are obtained by an emulsion method, allowing the preparation of spherical gel particles of controllable sizes with diameters in the mm or μm range. Microgels based on LMWG/alginate can be easily prepared with reproducible diameters <1 μm (ca. 800 nm). They are stable in water at room temperature for many months, and survive injection through a syringe. The rapid assembly of the LMWG on cooling plays an active role in helping control the diameter of the microgel beads. These LMWG microbeads retained the ability of the parent gel to deliver the bioactive molecule heparin, and in cell culture medium this enhanced the growth of human mesenchymal stem cells. Such microgels may therefore have future applications in tissue repair. This approach to fabricating LMWG microgels is a platform technology, which could potentially be applied to a variety of different functional LMWGs, and hence has wide-ranging potential.

We report microgel beads with diameters of ca. 800 nm based on interpenetrating networks of a low-molecular-weight gelator and a polymer gelator, and demonstrate their use as heparin delivery vehicles to enhance stem cell growth.     

Untersuchung von Milch und Molkereiprodukten

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Functional Interdependence in Coupled Dissipative Structures: Physical Foundations of Biological Coordination

Coordination within and between organisms is one of the most complex abilities of living systems, requiring the concerted regulation of many physiological constituents, and this complexity can be particularly difficult to explain by appealing to physics. A valuable framework for understanding biological coordination is the coordinative structure, a self-organized assembly of physiological elements that collectively performs a specific function. Coordinative structures are characterized by three properties: (1) multiple coupled components, (2) soft-assembly, and (3) functional organization. Coordinative structures have been hypothesized to be specific instantiations of dissipative structures, non-equilibrium, self-organized, physical systems exhibiting complex pattern formation in structure and behaviors. We pursued this hypothesis by testing for these three properties of coordinative structures in an electrically-driven dissipative structure. Our system demonstrates dynamic reorganization in response to functional perturbation, a behavior of coordinative structures called reciprocal compensation. Reciprocal compensation is corroborated by a dynamical systems model of the underlying physics. This coordinated activity of the system appears to derive from the system’s intrinsic end-directed behavior to maximize the rate of entropy production. The paper includes three primary components: (1) empirical data on emergent coordinated phenomena in a physical system, (2) computational simulations of this physical system, and (3) theoretical evaluation of the empirical and simulated results in the context of physics and the life sciences. This study reveals similarities between an electrically-driven dissipative structure that exhibits end-directed behavior and the goal-oriented behaviors of more complex living systems.     

Molecular structure and fracture properties of ZrO<Subscript>X</Subscript>/Epoxysilane hybrid films

The mechanical reliability of hybrid films depends critically on their fracture properties which are controlled largely by the film composition and molecular structure. We have investigated the adhesive and cohesive fracture properties of hybrid films processed from 3-glycidoxypropyltrimethoxysilane (GPTMS) and tetra n-propoxyzirconium (TPOZ), for which the roles of molecular structure and composition have not been well established. The influences of film Zr/GPTMS ratio, silane crosslinking, and substrate composition on fracture resistance were quantified in terms of the critical strain energy release rate, G_C Film fracture energy was found to increase, then decrease with increasing Zr/GPTMS ratio. Removal of the epoxy rings of GPTMS from the film was found to drastically decrease the cohesive fracture energy of the film as well as the adhesive fracture energy of the film/epoxy interface. Finally, films deposited on silicon had much higher fracture energies compared to those deposited onto aluminum and titanium from identical sols. FTIR, XPS, and AFM were used to characterize the film structure and fracture surfaces. The molecular-scale mechanisms responsible for the observed trends are discussed. These results provide new insights into the interaction between the substrate chemistry, molecular structure, and mechanical reliability of hybrid sol-gel films.     

Cross‐Reactive Sensor Arrays for the Detection of Peptides in Aqueous Solution by Fluorescence Spectroscopy

A simple but powerful method for the sensing of peptides in aqueous solution has been developed. The transition‐metal complexes [PdCl₂(en)], [{RhCl₂Cp*}₂], and [{RuCl₂(p‐cymene)}₂] were combined with six different fluorescent dyes to build a cross‐reactive sensor array. The fluorescence response of the individual sensor units was based on competitive complexation reactions between the peptide analytes and the fluorescent dyes. The collective response of the sensor array in a time‐resolved fashion was used as an input for multivariate analyses. A sensor array comprised of only six metal–dye combinations was able to differentiate ten different dipeptides in buffered aqueous solution at a concentration of 50 μM . Furthermore, the cross‐reactive sensor could be used to obtain information about the identity and the quantity of the pharmacologically interesting dipeptides carnosine and homocarnosine in a complex biological matrix, such as deproteinized human blood serum. The sensor array was also able to sense longer peptides, which was demonstrated by differentiating mixtures of the nonapeptide bradykinin and the decapeptide kallidin.     

Detecting the "afterglow" of 13C NMR in proteins using multiple receivers

We show that the weak signal that remains after (13)C-detected experiments (the (13)C "afterglow") can still be measured with high sensitivity by proton detection. This is illustrated by the incorporation of two experiments, 2D (HA)CACO and 3D (HA)CA(CO)NNH, into a single pulse sequence that makes use of two receivers in parallel. In cases where the sensitivity is not limiting, such as applications to small proteins, the inclusion of the projection-reconstruction method permits the recording of both spectra in only 15 min. High-quality data sets for the 143 residue nuclease A inhibitor (2 °C, correlation time 17.5 ns) were obtained in 3 h, illustrating the utility of the method even in studies of moderately sized proteins.