XRD-Studies of SiC/Si layers on carbon substrates

Structural investigations of thin films of SiC, SiC with free silicon and various titanium suicides (TiSi₂, TiSi and Ti₅Si₃) are described. The crystal phases have been identified using X-ray diffractometry. The growth of reaction products from surface reactions between silicon and deposited titanium can be observed.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Tuning single nucleotide discrimination in polymerase chain reactions (PCRs): synthesis of primer probes bearing polar 4'-C-modifications and their application in allele-specific PCR

There are many methods available for the detection of nucleotide variations in genetic material. Most of these methods are applied after amplification of the target genome sequence by the polymerase chain reaction (PCR). Many efforts are currently underway to develop techniques that can detect single nucleotide variations in genes either by means of, or without the need for, PCR. Allele-specific PCR (asPCR), which reports nucleotide variations based on either the presence or absence of a PCR-amplified DNA product, has the potential to combine target amplification and analysis in one single step. The principle of asPCR is based on the formation of matched or mismatched primer-target complexes by using allele-specific primer probes. PCR amplification by a DNA polymerase from matched 3'-primer termini proceeds, whereas a mismatch should obviate amplification. Given the recent advancements in real-time PCR, this technique should, in principle, allow single nucleotide variations to be detected online. However, this method is hampered by low selectivity, which necessitates tedious and costly manipulations. Recently, we reported that the selectivity of asPCR can be significantly increased through the employment of chemically modified primer probes. Here we report further significant advances in this area. We describe the synthesis of various primer probes that bear polar 4'-C-modified nucleotide residues at their 3' termini, and their evaluation in real-time asPCR. We found that primer probes bearing a 4'-C-methoxymethylene modification have superior properties in the discrimination of single nucleotide variations by PCR.     

Enantioselective, chirally templated sol-gel thin films

Enantioselective surfactant-templated thin films were fabricated through the sol-gel (SG) process. The enantioselectivity is general in the sense that it discriminates between pairs of enantiomers not used for the imprinting process. The chiral cationic surfactant (-)-N-dodecyl-N-methylephedrinium bromide (1) was used as the surfactant template, and after its extraction chiral domains were created. The chiral discriminative feature of these films was examined by challenging with pure enantiomer solutions for rebinding. Selective adsorption was shown using (R)- and (S)-propranolol, (R)-2 and (S)-2, respectively, and (R)- and (S)-2,2,2-trifluoro-1-(9-anthryl)ethanol, (R)-3 and (S)-3, respectively, as the chiral probes. The selective adsorption was measured by fluorescence analysis, and the chiral selectivity factors were found to be 1.6 for 2 and 2.25 for 3. In both cases, (R)-enantiomer was adsorbed preferably. The resulting material was characterized by transmission electron microscopy, by diffraction, and by surface area measurements, and was found to be semicrystalline with short-range ordered domains (50 A) of hexagonal symmetry.     

The modulation of face-face π-π interactions in Lewis acid catalysis

The enantiomeric excess observed for the exo-adduct from the Lewis acid catalysed Diels-Alder reaction between cyclopentadiene and methacrolein can be increased up to 21% by simple modification of the electronics of the aromatic ring in a series of stilbene-derived diol ligands, suggesting that the proposed face-face π-π interaction between the catalyst and the dienophile can be modulated by altering the electron density on the aromatic ring.     

Effect of ionic strength on the self-assembly, morphology and gelation of pH responsive β-sheet tape-forming peptides

Molecular self-assembly is an intrinsic property of proteins central to their biological functionality. One important industrially interesting property is the ability to control and switch on and off self-assembly using a variety of external chemical and physical triggers. Model peptides have been developed with significantly reduced chemical and structural complexity compared to biological proteins. These are ideal systems for exposing the fundamental principles that drive protein-like self-assembly, as well as for establishing in a quantitative manner their structure-function relationship. We investigate simple, short model peptides that adopt a purely β-strand conformation, align in an antiparallel manner and self-assemble in one dimension in solution into long β-sheet nanotapes and higher order aggregates with no other conformation (i.e., helices, turns or random coils) present in the aggregates. These micrometre-long nanostructures gel in solutions at concentrations as low as 0.2% v/v. Their gel-fluid transition has been previously shown to be controlled by pH, temperature, or by mixing with complementary peptides. Here we show the dramatic effect of another chemical trigger, that of physiological-like salt concentration, on the self-assembly, morphology and gelation of a series of systematically designed charged self-assembling tape-forming peptides, each 11 amino acid residues in length, in the pH range of 2-14. This study provides a detailed understanding of the self-assembly of this class of peptides in aqueous solutions of biologically relevant pH and ionic strength. This insight has led to the development of injectable self-assembling peptide lubricants as potential therapeutics for the treatment of early stage knee joint osteoarthritis.     

Gauge-independent quantization of the schr?dinger and radiation fields

The quantization of several Schrödinger fields interacting with the electromagnetic field is carried out without reference to a particular gauge. The canonical formalism requires a modification introduced by Dirac and Bergmann for constraints. The Coulomb interaction is separated from the radiation and it gives rise to bound states of atoms and molecules. Particle operators are represented in the usual manner in Fock space, while the radiation field can be described by state functionals. Constraints can be included in the canonical formalism by Lagrange multipliers, leading to results equivalent to those of Dirac and Bergmann.This work was supported in part by Drexel University