Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Diffusion of Gold Nanoparticles in Inverse Opals Probed by Heterodyne Dynamic Light Scattering

The diffusive behavior of nanoparticles inside porous materials is attracting a lot of interest in the context of understanding, modeling, and optimization of many technical processes. A very powerful technique for characterizing the diffusive behavior of particles in free media is dynamic light scattering (DLS). The applicability of the method in porous media is considered, however, to be rather difficult due to the presence of multiple sources of scattering. In contrast to most of the previous approaches, the DLS method was applied without ensuring matching refractive indices of solvent and porous matrix in the present study. To test the capabilities of the method, the diffusion of spherical gold nanoparticles within the interconnected, periodic nanopores of inverse opals was analyzed. Despite the complexity of this system, which involves many interfaces and different refractive indices, a clear signal related to the motion of particles inside the porous media was obtained. As expected, the diffusive process inside the porous sample slowed down compared to the particle diffusion in free media. The obtained effective diffusion coefficients were found to be wave vector-dependent. They increased linearly with increasing spatial extension of the probed particle concentration fluctuations. On average, the slowing-down factor measured in this work agrees within combined uncertainties with literature data.

     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

Teachers' beliefs on teacher training contents and related characteristics of implementation—the example of introducing the topic study method in mathematics classrooms

So-called “bottom-up” strategies for implementation based on mathematics teachers' own developmental activities are considered to be a powerful approach when encouraging teachers to introduce alternative instructional practices. For evaluational research of in-service teacher training programs using “bottom-up” implementation strategies, the way how teachers implement contents of the teacher training is at the centre of interest. As the teachers' active role in the implementation process is necessary, their individual beliefs on the contents of the teacher training and their expectancies might influence the teachers' implementational activities. These beliefs can be considered as components of professional knowledge and pedagogical contents knowledge (Shulman, 1986) in particular. For this reason, the study focuses on the development of beliefs on contents of a teacher training program throughout the training on the one hand and relationships with characteristics of implementation on the other hand. We consider the example of introducing a student-centred learning environment, the so-called topic study method, in the teachers' classrooms. The results indicate that there are interdependencies between beliefs on the teacher training contents and characteristics of implementation.     

Tunable microlens arrays using polymer network liquid crystal

A tunable-focus microlens array based on polymer network liquid crystal (PNLC) is demonstrated. The PNLC was prepared using an ultraviolet (UV) light exposure through a patterned photomask. The photocurable monomer in each of the UV exposed spot forms an inhomogeneous centro-symmetrical polymer network which acts as a lens when a homogeneous electric field is applied to the cell. The focal length of the microlens arrays is tunable with the applied voltage.     

Small silver particles in glass surface layers produced by sodium-silver ion exchange — their concentration and size depth profile

Small spherical silver particles in a surface layer of commercial flat glass were produced by means of sodium-silver ion exchange. In each volume element of the layer there is a Gaussian distribution of the particle diameters. The mean diameter increases with penetration depth. Within one individual sample it can vary from 4.5 nm immediately at the glass surface up to more than 50 nm at the end of the layer. Due to a special preparation technique the results were gained by microspectrophotometric measurements as well as by investigations carried out with the transmission electron microscope and the electron-probe microanalyzer on one and the same sample always as function of the penetration depth.     

Pentopyranosyl Oligonucleotide Systems. 9th Communication

Pyranosyl‐RNA (‘p‐RNA’ ) is an oligonucleotide system isomeric to natural RNA and composed of the very same building blocks as RNA. Its generational, chemical, and informational properties are deemed to be those of an alternative nucleic acid system that could have been a candidate in Nature's evolutionary choice of the molecular basis of genetic function. We consider the study of the chemistry of p‐RNA as etiologically relevant in the sense that knowledge of its structural, chemical, and informational properties on the chemical level offers both a perspective and reference points for the recognition of specific structural assets of the RNA structure that made it the (supposedly) superior system among possible alternatives and, therefore, the system that became part of biology as we know it today. The paper describes the chemical synthesis of β‐d‐ (and L )‐ribopyranosyl‐(4′→2′)‐oligonucleotide sequences, presents a resume of their structural and chemical properties, and cautiously discusses what we may and may not have learned from the pyranosyl isomer of RNA with respect to the conundrum of RNA's origin.     

Timelike Compton scattering: exclusive photoproduction of lepton pairs

We investigate the exclusive photoproduction of a heavy timelike photon which decays into a lepton pair, . This can be seen as the analog of deeply virtual Compton scattering, and we argue that the two processes are complementary for studying generalized parton distributions in the nucleon. In an unpolarized experiment the angular distribution of the leptons readily provides access to the real part of the Compton amplitude. We estimate the possible size of this effect in kinematics where the Compton process should be dominated by quark exchange. Received: 9 October 2001 / Published online: 5 April 2002