Structural transformations related to organic solid-state reactions: correlation studies of NMR and X-ray analysis

Eine zielgerichtete Steuerung und Durchführung von organischen Festkörperreaktionen wird unter anderem durch genaue Kenntnis von Packungseffekten ermöglicht. Im Rahmen dieser Arbeit konnte durch den kombinierten Einsatz von Einkristallröntgenanalyse und hochauf-lösender Festkörper-NMR an ausgewählten Beispielen ein tieferes Verständnis und Einblicke in die Reaktionsmechanismen von organischen Festkörperreaktionen auf molekularer Ebene gewonnen werden. So konnten bei der topotaktischen [2+2] Photodimerisierung von Zimt-säure Intermediate isoliert und strukturell charakterisiert werden. Insbesondere anhand statischer Deuteronen- und 13C-CPMAS NMR Spektren konnten eindeutig dynamische Wasserstoffbrücken nachgewiesen werden, die transient die Zentrosymmetrie des Reaktions-produkts aufheben. Ein weiterer Nachweis gelang daraufhin mittels Hochtemperatur-Röntgen-untersuchung, sodass der scheinbare Widerspruch von NMR- und Röntgenuntersuchungen gelöst werden konnte. Eine Veresterung der Zimtsäure entfernt diese Wasserstoffbrücken und erhält somit die Zentrosymmetrie des Photodimers. Weiterhin werden Ansätze zur Strukturkontrolle in Festkörpern basierend auf der molekularen Erkennung des Hydroxyl-Pyridin (OH-N) Heterosynthon in Co-Kristallen beschrieben, wobei vor allem die Stabilität des Synthons in Gegenwart funktioneller Gruppen mit Möglichkeit zu kompetetiver Wasserstoffbrückenbildung festgestellt wurde. Durch Erweiterung dieses Ansatzes wurde die molekulare Spezifität des Hydroxyl-Pyridin (OH-N) Heterosynthons bei gleichzeitiger Co-Kristallisation mit mehreren Komponenten erfolgreich aufgezeigt. Am Beispiel der Co-Kristallisation von trans--1,2-bis(4-pyridyl)ethylen (bpe) mit Resorcinol (res) in Gegenwart von trans-1,2-bis(4-pyridyl)ethan (bpet) konnten Zwischenprodukte der Fest-körperreaktionen und neuartige Polymorphe isoliert werden, wobei eine lückenlose Aufklärung des Reaktionswegs mittels Röntgenanalyse gelang. Dabei zeigte sich, dass das Templat Resorcinol aus den Zielverbindungen entfernbar ist. Ferner gelang die Durchführung einer seltenen, nicht-idealen Einkristall-Einkristall-Umlagerung von trans--1,2-bis(4-pyridyl)ethylen (bpe) mit Resorcinol (res). In allen Fällen konnten die Fragen zur Struktur und Dynamik der untersuchten Verbindungen nur durch gemeinsame Nutzung von Röntgenanalyse und NMR-Spektroskopie bei vergleichbaren Temperaturen eindeutig und umfassend geklärt werden.

Teeth restored using fiber-reinforced posts: in vitro fracture tests and finite element analysis

In dentistry the restoration of decayed teeth is challenging and makes great demands on both the dentist and the materials. Hence, fiber-reinforced posts have been introduced. The effects of different variables on the ultimate load on teeth restored using fiber-reinforced posts is controversial, maybe because the results are mostly based on non-standardized in vitro tests and, therefore, give inhomogeneous results. This study combines the advantages of in vitro tests and finite element analysis (FEA) to clarify the effects of ferrule height, post length and cementation technique used for restoration. Sixty-four single rooted premolars were decoronated (ferrule height 1 or 2 mm), endodontically treated and restored using fiber posts (length 2 or 7 mm), composite fillings and metal crowns (resin bonded or cemented). After thermocycling and chewing simulation the samples were loaded until fracture, recording first damage events. Using UNIANOVA to analyze recorded fracture loads, ferrule height and cementation technique were found to be significant, i.e. increased ferrule height and resin bonding of the crown resulted in higher fracture loads. Post length had no significant effect. All conventionally cemented crowns with a 1-mm ferrule height failed during artificial ageing, in contrast to resin-bonded crowns (75% survival rate). FEA confirmed these results and provided information about stress and force distribution within the restoration. Based on the findings of in vitro tests and computations we concluded that crowns, especially those with a small ferrule height, should be resin bonded. Finally, centrally positioned fiber-reinforced posts did not contribute to load transfer as long as the bond between the tooth and composite core was intact.

Bonding of restorative materials to dentin with various luting agents

The aim was to compare eight types of luting agents when used to bond six indirect, laboratory restorative materials to dentin. Cylinders of the six restorative materials (Esteticor Avenir [gold alloy], Tritan [titanium], NobelRondo [feldspathic porcelain], Finesse All-Ceramic [leucite-glass ceramic], Lava [zirconia], and Sinfony [resin composite]) were ground and air-abraded. Cylinders of feldspathic porcelain and glass ceramic were additionally etched with hydrofluoric acid and were silane-treated. The cylinders were luted to ground human dentin with eight luting agents (DeTrey Zinc [zinc phosphate cement], Fuji I [conventional glass ionomer cement], Fuji Plus [resin-modified glass ionomer cement], Variolink II [conventional etch-and-rinse resin cement], Panavia F2.0 and Multilink [self-etch resin cements], and RelyX Unicem Aplicap and Maxcem [self-adhesive resin cements]). After water storage at 37°C for one week, the shear bond strength of the specimens (n=8/group) was measured, and the fracture mode was stereomicroscopically examined. Bond strength data were analyzed with two-factorial analysis of variance (ANOVA) followed by Newman-Keuls' Multiple Range Test (?=0.05). Both the restorative material and the luting agent had a significant effect on bond strength, and significant interaction was noted between the two variables. Zinc phosphate cement and glass ionomer cements produced the lowest bond strengths, whereas the highest bond strengths were found with the two self-etch and one of the self-adhesive resin cements. Generally, the fracture mode varied markedly with the restorative material. The luting agents had a bigger influence on bond strength between restorative materials and dentin than was seen with the restorative material.

British Monetary Sovereignty: A Cultural Analysis

In this thesis, I will document and analyze historical aspects of the British debate over adopting a common currency with the European Community primarily during the last half of the twentieth century until the present. More specifically, while on the surface such a decision would seem to turn on economic or political considerations, I will show that this historic British decision not to surrender their pound sterling in exchange for the euro was rooted in the nation's cultural identity. During this decades long British debate over the euro, two opposing, but strongly held, positions developed; one side believed that Britain had a compelling interest in bonding with the rest of Europe economically as well as politically, the other side believed that Britain's independent heritage was deeply rooted in many of its traditions including maintaining control of its own monetary matters, which included keeping its pound sterling. As part of this thesis, I have conducted interviews with business leaders, economists, and social scientists as well as researched public records in order to assess many of the arguments favoring and opposing Britain's adoption of the euro. Many Britons strongly believed that it was time to join other Europeans, who were willing to sacrifice their sovereign currency to a bold common currency experiment, while other Britons viewed the pound sterling as too integral a part of British heritage to abandon. Ultimately, British leaders and citizens had to determine whether such a currency tradeoff would be worth it to them as a nation. It was a gamble that twelve other nations (at the time of the euro's 2002 launch) were ready to take, optimistically calculating that easier credit and reduced exchange transaction costs would lead to greater economic prosperity. Many asserted that only with ! ! such a united European monetary coalition would Europe's nations be able to compete trade-wise with powerful economic nations like the United States and China. My conclusion is that Britain's refusal to join the euro was a decision that had less to do with economic opportunity or political motivations and much more to do with how the British people viewed themselves culturally and their identity as an independent nation.

The bonding of glass ionomer cements to caries-affected primary tooth dentin

PURPOSE The purpose of this study was to evaluate the bonding of glass ionomer cements (GICs) to sound and caries-affected dentin by microtensile bond strength (μTBS) and nanoleakage (NL) tests. METHODS Occlusal cavity preparations were made in 36 sound primary molars. Half of the specimens were submitted to a pH-cycling model to create simulated caries-affected dentin. Teeth were randomly restored with one of the three materials: (1) resin-modified GIC with nanoparticles (Ketac N100; KN); (2) resin-modified GIC (Vitremer; VI); and (3) high-viscosity GIC (Ketac Molar Easy Mix; KM). Specimens were tested using a microtensile test (1 mm/minute). One specimen from each tooth was immersed in ammoniacal silver nitrate for 24 hours and revealed after eight hours to assess interfacial NL. The μTBS means were analyzed by 2-way analysis of variance and Tukey's post hoc test. For NL, Kruskal-Wallis and Mann-Whitney tests were used (P<.05). RESULTS No difference was found between sound and caries-affected dentin (P>.05). KM showed the lowest GIC-dentin μTBS values, while VI and KN showed higher values. Infiltration of ammoniacal silver nitrate into the adhesive interface was not affected by sound or caries-affected dentin. CONCLUSION Caries-affected dentin does not jeopardize the bonding of glass ionomer cements to primary tooth dentin.

Three strategically placed hydrogen-bonding residues convert a proton pump into a sensory receptor.

In haloarchaea, light-driven ion transporters have been modified by evolution to produce sensory receptors that relay light signals to transducer proteins controlling motility behavior. The proton pump bacteriorhodopsin and the phototaxis receptor sensory rhodopsin II (SRII) differ by 74% of their residues, with nearly all conserved residues within the photoreactive retinal-binding pocket in the membrane-embedded center of the proteins. Here, we show that three residues in bacteriorhodopsin replaced by the corresponding residues in SRII enable bacteriorhodopsin to efficiently relay the retinal photoisomerization signal to the SRII integral membrane transducer (HtrII) and induce robust phototaxis responses. A single replacement (Ala-215-Thr), bridging the retinal and the membrane-embedded surface, confers weak phototaxis signaling activity, and the additional two (surface substitutions Pro-200-Thr and Val-210-Tyr), expected to align bacteriorhodopsin and HtrII in similar juxtaposition as SRII and HtrII, greatly enhance the signaling. In SRII, the three residues form a chain of hydrogen bonds from the retinal's photoisomerized C(13)=C(14) double bond to residues in the membrane-embedded alpha-helices of HtrII. The results suggest a chemical mechanism for signaling that entails initial storage of energy of photoisomerization in SRII's hydrogen bond between Tyr-174, which is in contact with the retinal, and Thr-204, which borders residues on the SRII surface in contact with HtrII, followed by transfer of this chemical energy to drive structural transitions in the transducer helices. The results demonstrate that evolution accomplished an elegant but simple conversion: The essential differences between transport and signaling proteins in the rhodopsin family are far less than previously imagined.

Composition Space Analysis in the Development of Copper Molybdate Hybrids Decorated by a Bifunctional Pyrazolyl/1,2,4-Triazole Ligand

A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

BPA qualtitative and quantitative assessment associated with orthodontic bonding in vivo

OBJECTIVE To assess the in vivo amount of BPA released from a visible light-cured orthodontic adhesive, immediately after bracket bonding. METHODS 20 orthodontic patients were recruited after obtaining informed consent. All patients received 24 orthodontic brackets in both dental arches. In Group A (11 patients), 25 ml of tap water were used for mouth rinsing, whereas in Group B (9 patients) a simulated mouth rinse formulation was used: a mixture of 20 ml de-ionized water plus 5 ml absolute ethanol. Rinsing solutions were collected before, immediately after placing the orthodontic appliances and after washing out the oral cavity and were then stored in glass tubes. Rinsing was performed in a single phase for 60s with the entire volume of each liquid. The BPA analysis was performed by gas chromatography-mass spectrometry. RESULTS An increase in BPA concentration immediately after the 1st post-bonding rinse was observed, for both rinsing media, which was reduced after the 2nd post-bonding rinse. Water exhibited higher levels of BPA concentration than water/ethanol after 1st and 2nd post-bonding rinses. Two-way mixed Repeated Measures ANOVA showed that the primary null hypothesis declaring mean BPA concentration to be equal across rinsing medium and rinsing status was rejected (p-value <0.001). The main effects of the rinsing medium and status, as well as their interaction were found to be statistically significant (p-values 0.048, <0.001 and 0.011 respectively). SIGNIFICANCE A significant pattern of increase of BPA concentration, followed by a decrease that reached the initial values was observed. The amount of BPA was relatively low and far below the reference limits of tolerable daily intake.

New perspectives on quantitative textural analysis

Process mineralogy provides the mineralogical information required by geometallurgists to address the inherent variation of geological data. The successful benefitiation of ores mostly depends on the ability of mineral processing to be efficiently adapted to the ore characteristics, being liberation one of the most relevant mineralogical parameters. The liberation characteristics of ores are intimately related to mineral texture. Therefore, the characterization of liberation necessarily requieres the identification and quantification of those textural features with a major bearing on mineral liberation. From this point of view grain size, bonding between mineral grains and intergrowth types are considered as the most influential textural attributes. While the quantification of grain size is a usual output of automated current technologies, information about grain boundaries and intergrowth types is usually descriptive and difficult to quantify to be included in the geometallurgical model. Aiming at the systematic and quantitative analysis of the intergrowth type within mineral particles, a new methodology based on digital image analysis has been developed. In this work, the ability of this methodology to achieve a more complete characterization of liberation is explored by the analysis of chalcopyrite in the rougher concentrate of the Kansanshi copper-gold mine (Zambia). Results obtained show that the method provides valuable textural information to achieve a better understanding of mineral behaviour during concentration processes. The potential of this method is enhanced by the fact that it provides data unavailable by current technologies. This opens up new perspectives on the quantitative analysis of mineral processing performance based on textural attributes.

Protein–RNA interactions: a structural analysis

A detailed computational analysis of 32 protein–RNA complexes is presented. A number of physical and chemical properties of the intermolecular interfaces are calculated and compared with those observed in protein–double-stranded DNA and protein–single-stranded DNA complexes. The interface properties of the protein–RNA complexes reveal the diverse nature of the binding sites. van der Waals contacts played a more prevalent role than hydrogen bond contacts, and preferential binding to guanine and uracil was observed. The positively charged residue, arginine, and the single aromatic residues, phenylalanine and tyrosine, all played key roles in the RNA binding sites. A comparison between protein–RNA and protein–DNA complexes showed that whilst base and backbone contacts (both hydrogen bonding and van der Waals) were observed with equal frequency in the protein–RNA complexes, backbone contacts were more dominant in the protein–DNA complexes. Although similar modes of secondary structure interactions have been observed in RNA and DNA binding proteins, the current analysis emphasises the differences that exist between the two types of nucleic acid binding protein at the atomic contact level.

Structural Analysis and Molecular Model of a Self-Incompatibility RNase from Wild Tomato1

Self-incompatibility RNases (S-RNases) are an allelic series of style glycoproteins associated with rejection of self-pollen in solanaceous plants. The nucleotide sequences of S-RNase alleles from several genera have been determined, but the structure of the gene products has only been described for those from Nicotiana alata. We report on the N-glycan structures and the disulfide bonding of the S3-RNase from wild tomato (Lycopersicon peruvianum) and use this and other information to construct a model of this molecule. The S3-RNase has a single N-glycosylation site (Asn-28) to which one of three N-glycans is attached. S3-RNase has seven Cys residues; six are involved in disulfide linkages (Cys-16-Cys-21, Cys-46-Cys-91, and Cys-166-Cys-177), and one has a free thiol group (Cys-150). The disulfide-bonding pattern is consistent with that observed in RNase Rh, a related RNase for which radiographic-crystallographic information is available. A molecular model of the S3-RNase shows that four of the most variable regions of the S-RNases are clustered on one surface of the molecule. This is discussed in the context of recent experiments that set out to determine the regions of the S-RNase important for recognition during the self-incompatibility response.

Direct measurement of hydrogen bonding in DNA nucleotide bases by atomic force microscopy.

We have used self-assembled purines and pyrimidines on planar gold surfaces and on gold-coated atomic force microscope (AFM) tips to directly probe intermolecular hydrogen bonds. Electron spectroscopy for chemical analysis (ESCA) and thermal programmed desorption (TPD) measurements of the molecular layers suggested monolayer coverage and a desorption energy of about 25 kcal/mol. Experiments were performed under water, with all four DNA bases immobilized on AFM tips and flat surfaces. Directional hydrogen-bonding interaction between the tip molecules and the surface molecules could be measured only when opposite base-pair coatings were used. The directional interactions were inhibited by excess nucleotide base in solution. Nondirectional van der Waals forces were present in all other cases. Forces as low as two interacting base pairs have been measured. With coated AFM tips, surface chemistry-sensitive recognition atomic force microscopy can be performed.

Analysis of the free vibration of rectangular plates with central cut-outs using the discrete Ritz method

We present an analysis of the free vibration of plates with internal discontinuities due to central cut-outs. A numerical formulation for a basic L-shaped element which is divided into appropriate sub-domains that are dependent upon the location of the cut-out is used as the basic building element. Trial functions formed to satisfy certain boundary conditions are employed to define the transverse deflection of each sub-domain. Mathematical treatments in terms of the continuities in displacement, slope, moment, and higher derivatives between the adjacent sub-domains are enforced at the interconnecting edges. The energy functional results, from the proper assembly of the coupled strain and kinetic energy contributions of each sub-domain, are minimized via the Ritz procedure to extract the vibration frequencies and. mode shapes of the plates. The procedures are demonstrated by considering plates with central cut-outs that are subjected to two types of boundary conditions. (C) 2003 Elsevier Ltd. All rights reserved.

Depression in young adolescents: Investigations using 2 and 3 factor versions of the parental bonding instrument

Associations between parenting style and depressive symptomatology in a community sample of young adolescents (N = 2596) were investigated using self-report measures including the Parental Bonding Instrument and the Center for Epidemiologic Studies Depression Scale. Specifically, the 25-item 2-factor and 3-factor models by Parker et al. (1979), Kendler's (1996) 16-item 3-factor model, and Parker's (1983) quadrant model for the Parental Bonding Instrument were compared. Data analysis included analysis of variance and logistic regression. Reanalysis of Parker's original scale indicates that overprotection is composed of separate factors: intrusiveness (at the individual level) and restrictiveness (in the social context). All models reveal significant independent contributions from paternal care, maternal care, and maternal overprotection (2-factor) or intrusiveness (3-factor) to moderate and serious depressive symptomatology, controlling for sex and family living arrangement. Additive rather than multiplicative interactions between care and overprotection were found. Regardless of the level of parental care and affection, clinicians should note that maternal intrusiveness is strongly associated with adverse psychosocial health in young adolescents.