A stochastic principle behind polar properties of condensed molecular matter

A statistical mechanics view leads to the conclusion that polar molecules allowed to populate a degree of freedom for orientational disorder in a condensed phase thermalize into a bi-polar state featuring zero net polarity. In cases of orientational disorder polar order of condensed molecular matter can only exist in corresponding sectors of opposite average polarities. Channel type inclusion compounds, single component molecular crystals, solid solutions, optically anomalous crystals, inorganic ionic crystals, biomimetic crystals and biological tissues investigated by scanning pyroelectric and phase sensitive second harmonic generation microscopy all showed domains of opposite polarities in their final grown state. For reported polar molecular crystal structures it is assumed that kinetic hindrance along one direction of the polar axis is preventing the formation of a bi-polar state, thus allowing for a kinetically controlled mono-domain state. In this review we summarize theoretical and experimental findings leading to far reaching conclusions on the polar state of solid molecular matter. “… no stationary state … of a system has an electrical dipole moment.” P. W. Anderson, Science, 1972, 177, 393.

Design-based stereology to quantify structural properties of artificial and natural snow using thin sections

The quantification of the structural properties of snow is traditionally based on model-based stereology. Model-based stereology requires assumptions about the shape of the investigated structure. Here, we show how the density, specific surface area, and grain boundary area can be measured using a design-based method, where no assumptions about structural properties are necessary. The stereological results were also compared to X-ray tomography to control the accuracy of the method. The specific surface area calculated with the stereological method was 19.8 ± 12.3% smaller than with X-ray tomography. For the density, the stereological method gave results that were 11.7 ± 12.1% larger than X-ray tomography. The statistical analysis of the estimates confirmed that the stereological method and the sampling used are accurate. This stereological method was successfully tested on artificially produced ice beads but also on several snow types. Combining stereology and polarisation microscopy provides a good estimate of grain boundary areas in ice beads and in natural snow, with some limitatio

Unanticipated structural and functional properties of delta-subunit-containing GABAA receptors

GABA(A) receptors mediate inhibitory neurotransmission in the mammalian brain via synaptic and extrasynaptic receptors. The delta (delta)-subunit-containing receptors are expressed exclusively extra-synaptically and mediate tonic inhibition. In the present study, we were interested in determining the architecture of receptors containing the delta-subunit. To investigate this, we predefined the subunit arrangement by concatenation. We prepared five dual and three triple concatenated subunit constructs. These concatenated dual and triple constructs were used to predefine nine different GABA(A) receptor pentamers. These pentamers composed of alpha(1)-, beta(3)-, and delta-subunits were expressed in Xenopus oocytes and maximal currents elicited in response to 1 mm GABA were determined in the presence and absence of THDOC (3alpha, 21-dihydroxy-5alpha-pregnane-20-one). beta(3)-alpha(1)-delta/alpha(1)-beta(3) and beta(3)-alpha(1)-delta/beta(3)-alpha(1) resulted in the expression of large currents in response to GABA. Interestingly, the presence of the neurosteroid THDOC uncovered alpha(1)-beta(3)-alpha(1)/beta(3)-delta receptors, additionally. The functional receptors were characterized in detail using the agonist GABA, THDOC, Zn(2+), and ethanol and their properties were compared with those of non-concatenated alpha(1)beta(3) and alpha(1)beta(3)delta receptors. Each concatenated receptor isoform displayed a specific set of properties, but none of them responded to 30 mm ethanol. We conclude from the investigated receptors that delta can assume multiple positions in the receptor pentamer. The GABA dose-response properties of alpha(1)-beta(3)-alpha(1)/beta(3)-delta and beta(3)-alpha(1)-delta/alpha(1)-beta(3) match most closely the properties of non-concatenated alpha(1)beta(3)delta receptors. Furthermore, we show that the delta-subunit can contribute to the formation of an agonist site in alpha(1)-beta(3)-alpha(1)/beta(3)-delta receptors.

Does the (structural) context matter? Analysing individual and structural factors of members’ commitment to sports clubs

Introduction: Over the last decades, Swiss sports clubs have lost their "monopoly" in the market for sports-related services and increasingly are in competition with other sports providers. For many sport clubs long-term membership cannot be seen as a matter of course. Current research on sports clubs in Switzerland – as well as for other European countries – confirms the increasing difficulties in achieving long-term member commitment. Looking at recent findings of the Swiss sport clubs report (Lamprecht, Fischer & Stamm, 2012), it can be noted, that a decrease in memberships does not equally affect all clubs. There are sports clubs – because of their specific situational and structural conditions – that have few problems with member fluctuation, while other clubs show considerable declines in membership. Therefore, a clear understanding of individual and structural factors that trigger and sustain member commitment would help sports clubs to tackle this problem more effectively. This situation poses the question: What are the individual and structural determinants that influence the tendency to continue or to quit the membership? Methods: Existing research has extensively investigated the drivers of members’ commitment at an individual level. As commitment of members usually occurs within an organizational context, the characteristics of the organisation should be also considered. However, this context has been largely neglected in current research. This presentation addresses both the individual characteristics of members and the corresponding structural conditions of sports clubs resulting in a multi-level framework for the investigation of the factors of members’ commitment in sports clubs. The multilevel analysis grant a adequate handling of hierarchically structured data (e.g., Hox, 2002). The influences of both the individual and context level on the stability of memberships are estimated in multi-level models based on a sample of n = 1,434 sport club members from 36 sports clubs. Results: Results of these multi-level analyses indicate that commitment of members is not just an outcome of individual characteristics, such as strong identification with the club, positively perceived communication and cooperation, satisfaction with sports clubs’ offers, or voluntary engagement. It is also influenced by club-specific structural conditions: stable memberships are more probable in rural sports clubs, and in clubs that explicitly support sociability, whereas sporting-success oriented goals in clubs have a destabilizing effect. Discussion/Conclusion: The proposed multi-level framework and the multi-level analysis can open new perspectives for research concerning commitment of members to sports clubs and other topics and problems of sport organisation research, especially in assisting to understand individual behavior within organizational contexts. References: Hox, J. J. (2002). Multilevel analysis: Techniques and applications. Mahwah: Lawrence Erlbaum. Lamprecht, M., Fischer, A., & Stamm, H.-P. (2012). Die Schweizer Sportvereine – Strukturen, Leistungen, Herausforderungen. Zurich: Seismo.

Structural elucidation and antisense properties of a sugar-modified DNA analogue

Antisense oligonucleotides deserve great attention as potential drug candidates for the treatment of genetic disorders. For example, muscle dystrophy can be treated successfully in mice by antisense-induced exon skipping in the pre-mRNA coding for the structural protein dystrophin in muscle cells. For this purpose a sugar- and backbone-modified DNA analogue was designed, in which a tricyclic ring system substitutes the deoxyribose. These chemical modifications stabilize the dimers formed with the targeted RNA relative to native nucleic acid duplexes and increase the biostability of the antisense oligonucleotide. While evading enzymatic degradation constitutes an essential property of antisense oligonucleotides for therapeutic application, it renders the oligonucleotide inaccessible to biochemical sequencing techniques and requires the development of alternative methods based on mass spectrometry. The set of sequences studied includes tcDNA oligonucleotides ranging from 10 to 15 nucleotides in length as well as their hybrid duplexes with DNA and RNA complements. All samples were analyzed on a LTQ Orbitrap XL instrument equipped with a nano-electrospray source. For tandem mass spectrometric experiments collision-induced dissociation was performed, using helium as collision gas. Mass spectrometric sequencing of tcDNA oligomers manifests the applicability of the technique to substrates beyond the scope of enzyme-based methods. Sequencing requires the formation of characteristic backbone fragments, which take the form of a-B- and w-ions in the product ion spectra of tcDNA. These types of product ions are typically associated with unmodified DNA, which suggests a DNA-like fragmentation mechanism in tcDNA. The loss of nucleobases constitutes the second prevalent dissociation pathway observed in tcDNA. Comparison of partially and fully modified oligonucleotides indicates a pronounced impact of the sugar-moiety on the base loss. As this event initiates cleavage of the backbone, the presented results provide new mechanistic insights into the fragmentation of DNA in the gas-phase. The influence of the sugar-moiety on the dissociation extends to tcDNA:DNA and tcDNA:RNA hybrid duplexes, where base loss was found to be much more prominent from sugar-modified oligonucleotides than from their natural complements. Further prominent dissociation channels are strand separation and backbone cleavage of the single strands, as well as the ejection of backbone fragments from the intact duplex. The latter pathway depends noticeably on the base sequence. Moreover, it gives evidence of the high stability of the hybrid dimers, and thus directly reflects the affinity of tcDNA for its target in the cell. As the cellular target of tcDNA is a pre-mRNA, the structure was designed to discriminate RNA from DNA complements, which could be demonstrated by mass spectrometric experiments.

Conformationally Controlled Electron Delocalization in n-Type Rods: Synthesis, Structure, and Optical, Electrochemical, and Spectroelectrochemical Properties of Dicyanocyclophanes

A series of dicyanobiphenyl-cyclophanes 1-6 with various pi-backbone conformations and characteristic n-type semiconductor properties is presented. Their synthesis, optical, structural, electrochemical, spectroelectrochemical, and packing properties are investigated. The X-ray crystal structures of all n-type rods allow the systematic correlation of structural features with physical properties. In addition, the results are supported by quantum mechanical calculations based on density functional theory. A two-step reduction process is observed for all n-type rods, in which the first step is reversible. The potential gap between the reduction processes depends linearly on the cos(2) value of the torsion angle phi between the pi-systems. Similarly, optical absorption spectroscopy shows that the vertical excitation energy of the conjugation band correlates with the cos(2) value of the torsion angle phi. These correlations demonstrate that the fixed intramolecular torsion angle phi is the dominant factor determining the extent of electron delocalization in these model compounds, and that the angle phi measured in the solid-state structure is a good proxy for the molecular conformation in solution. Spectroelectrochemical investigations demonstrate that conformational rigidity is maintained even in the radical anion form. In particular, the absorption bands corresponding to the SOMO-LUMO+i transitions are shifted bathochromically, whereas the absorption bands corresponding to the HOMO-SOMO transition are shifted hypsochromically with increasing torsion angle phi.

An investigation into the mechanical and aesthetic properties of new generation coated nickel-titanium wires in the as-received state and after clinical use.

BACKGROUND/OBJECTIVES The purpose of this study was to compare the mechanical, structural, and aesthetic properties of two types of aesthetic coated nickel-titanium (NiTi) wires compared with comparable regular NiTi wires in the as-received state and after clinical use. MATERIALS/METHODS Sixty one subjects were randomly assigned to four groups (N = 61), two groups of coated wires and two groups of comparable, non-coated controls (n = 15/group). The period in the mouth ranged from 4 to 12 weeks after insertion. In total, 121 wires (61 retrieved and 60 as-received) were used in the study. The percentages of coating retention and loss were extrapolated from scans. A brief survey of five questions with three choices was given to all patients. Differential scanning calorimetry (DSC) and three-point bending tests were done on as-received and used wires. RESULTS The surface characterization by the percentage of resin remaining indicated that most wires in both test groups lost a significant amount of coating. A patient survey indicated that this was a noticeable feature for patients. DSC analysis of the wires indicated that the metallurgical properties of the coated wires were not similar to the uncoated wires in the as-received condition. Three-point bending results indicate a wide variation in test results with large standard deviations among all the groups. LIMITATIONS The extent of coating loss requires investigating, as do the biological properties of the detached coating. CONCLUSIONS Both wires lost a significant amount of aesthetic coating after varying periods in the mouth. The metallurgical testing of these findings may indicate that these wires perform differently in the mouth.

Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (‘Bicyclo-DNA’). Part 5. Synthesis, Characterization, and Pairing Properties of Oligo-αlpha-D-(bicyclodeoxynucleotides) of the Bases Adenine and Thymine (αlpha-Bicyclo-DNA)

10.1002/hlca.19950780816.abs A conformational analysis of the (3′S,5′R)-2′-deoxy-3′,5′-ethano-α-D-ribonucleosides (a-D-bicyclodeoxynucleosides) based on the X-ray analysis of N4-benzoyl-α-D-(bicyclodeoxycytidine) 6 and on 1H-NMR analysis of the α-D-bicyclodeoxynucleoside derivatives 1-7 reveals a rigid sugar structure with the furanose units in the l′-exo/2′-endo conformation and the secondary OH groups on the carbocyclic ring in the pseudoequatorial orientation. Oligonucleotides consisting of α-D-bicyclothymidine and α-D-bicyclodeoxyadenosine were successfully synthesized from the corresponding nucleosides by phosphoramidite methodology on a DNA synthesizer. An evaluation of their pairing properties with complementary natural RNA and DNA by means of UV/melting curves and CD spectroscopy show the following characteristics: i) α-bcd(A10) and α-bcd(T10) (α = short form of α-D)efficiently form complexes with complementary natural DNA and RNA. The stability of these hybrids is comparable or slightly lower as those with natural β-d(A10) or β-d(T10)( β = short form ofβ-D). ii) The strand orientation in α-bicyclo-DNA/β-DNA duplexes is parallel as was deduced from UV/melting curves of decamers with nonsymmetric base sequences. iii) CD Spectroscopy shows significant structural differences between α-bicyclo-DNA/β-DNA duplexes compared to α-DNA/β-DNA duplexes. Furthermore, α-bicyclo-DNA is ca. 100-fold more resistant to the enzyme snake-venom phosphodiesterase with respect to β-DNA and about equally resistant as α-DNA.

Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts

A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)2] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N–N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235–350 °C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 °C. Catalytic performances were influenced by the different acidic–basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.